Polymer composition having photoalignable group, liquid crystal alignment film formed of the polymer composition, and optical device having phase difference plate formed of the liquid crystal alignment film

ABSTRACT

To provide a photoalignable material that can yield a photoalignable film having a high optical uniformity and no alignment defect, and is excellent in sensitivity to allow photoalignment even with exposure in a short period of time, and a liquid crystal alignment film having a high alignment stability of a liquid crystal compound from the photoalignable material. A photoalignable polymer composition containing a specific photoalignable polymer and a specific polymer that is reactive with the photoalignable polymer is manufactured, and the photoalignable film is manufactured by applying the polymer composition onto a base material or the like, drying the applied composition thereon, and irradiating the dried composition with light. Furthermore, the liquid crystal alignment film is manufactured by allowing alignment of molecules of the liquid crystal compound in the photoalignment film.

TECHNICAL FIELD

The present invention relates to a photoalignable polymer composition, aliquid crystal alignment film formed of the polymer composition, anoptical film having the liquid crystal alignment film, and an opticaldevice such as a liquid crystal display device having the optical film.More specifically, the invention relates to a photoalignable polymercomposition having a low refractive index, and an excellenttransparency, liquid crystal alignment ability, solvent resistance andheat resistance, and an application using the same to an optical use.The photoalignable polymer composition of the invention is suitableparticularly for a patterned phase difference plate used for a passiveglasses 3D display, a built-in phase difference plate in a liquidcrystal display, a color filter overcoat having an optical alignmentfunction, or the like.

BACKGROUND ART

A liquid crystal display device is used in various kinds of liquidcrystal display units, including a monitor of a notebook-sized personalcomputer or a desktop personal computer, a viewfinder of a video camera,a projection display and a television. The liquid crystal display deviceis further utilized as an optoelectronics-related device such as anoptical printer head, an optical Fourier transformation device and alight valve. As a liquid crystal display device that has been applied sofar, a display device using a nematic liquid crystal is predominantlyapplied, and a practical application has been made for a liquid crystaldisplay device having a twisted nematic (TN) mode in which a directionof alignment of liquid crystals in the vicinity of one substrate, and adirection of alignment of liquid crystals in the vicinity of the othersubstrate are twisted at an angle of 90 degrees, a super twisted nematic(STN) mode in which the directions of alignment are ordinarily twistedat an angle of 180 degrees or more, or a so-called thin-film-transistor(TFT) mode in which a thin-film transistor is used.

However, a viewing angle at which an image can be properly visuallyrecognized is narrow in the liquid crystal display devices, and when theimage is viewed from an oblique direction, luminance and contrast may beoccasionally decreased, and luminance inversion may be occasionallycaused in a halftone. The issue of the viewing angle has been recentlyimproved by a liquid crystal display device having a TN mode in which anoptical compensation film is used, a multi-domain vertical alignment(MVA) mode in which a technology of vertical alignment and a technologyof protrusion structure are simultaneously applied (see Patentliterature No. 1), an in-plane switching (IPS) mode according to atransverse electric mode (see Patent literature No. 2), or the like.

A development of technology on the liquid crystal display device hasbeen achieved not only by an improvement of a driving mode and a devicestructure as described above but also by an improvement of a componentused for the display device. Among the components used for the displaydevice, in particular, a liquid crystal alignment film is one ofimportant elements relating to a display quality of the liquid crystaldisplay device, and a role of the liquid crystal alignment film becomesincreasingly important with achieving a high quality of the displaydevice year by year.

The liquid crystal alignment film is required to uniformly controlalignment of molecules of liquid crystals for developing uniform displaycharacteristics in the liquid crystal display device. Therefore, theliquid crystal alignment film is required to uniformly align liquidcrystal molecules on a substrate in one direction to further develop afixed tilt angle (pretilt angle) from a substrate surface.

Moreover, in order to realize an improvement in contrast and extensionof a viewing angle range in the image display unit, as an opticalcompensation film or a phase difference film, for example, a stretchedfilm having refractive index anisotropy or a film prepared by aligningand polymerizing a polymerizable liquid crystal compound is used.

In general, the liquid crystal alignment film is formed using a liquidcrystal aligning agent. The liquid crystal aligning agent that is mainlyused is currently in the form of a solution prepared by dissolvingpolyamic acid or soluble polyimide into an organic solvent. Such asolution is applied to the substrate, and then a film is formed by ameans such as heating, and thus a polyimide liquid crystal alignmentfilm is formed. Various kinds of liquid crystal aligning agents otherthan polyamic acid are also examined, however, are seldom practicallyutilized in view of heat resistance, chemical resistance (resistance toliquid crystals), applicability, liquid crystal alignment properties,electric characteristics, optical characteristics, displaycharacteristics and so forth.

Industrially, a rubbing method that is simple and allows high-speedtreatment in a large area is widely applied as an alignment treatmentmethod. The rubbing method applies treatment for rubbing a surface ofthe liquid crystal alignment film in one direction by using a fabricprepared by transplanting fibers of nylon, rayon, polyester or the like,and a uniform alignment of the liquid crystal molecules can be obtainedby the treatment. However, dust or static electricity generation or thelike is caused by the rubbing method. Thus, an alignment defect or aninfluence of dust or static electricity generation on the liquid crystaldevice is regarded as a problem. Moreover, in the case of a patternedphase difference film, control of an alignment pattern by the rubbingtreatment is difficult.

Consequently, a development has recently been made for a liquid crystalalignment control method in place of the rubbing treatment. With regardto a photoalignment method by which alignment treatment is applied byirradiation with light, many alignment mechanisms have been proposed,such as a photolysis method, a photoisomerization method, aphotodimerization method and a photocrosslinking method (see Patentliterature No. 3, Patent literature No. 4, Patent literature No. 5 andPatent literature No. 6.). The photoalignment method applies non-contactalignment, which is different from the rubbing method. In principle, asmaller amount of dust or static electricity is generated by thephotoalignment method, as compared with the rubbing treatment.

An improvement in performance as the liquid crystal display device canbe expected by controlling a state of alignment of molecules in a liquidcrystal monomolecular layer in contact with the liquid crystal alignmentfilm by using a liquid crystal alignment film having good alignmentproperties to which the alignment treatment is applied by thephotoalignment method.

A passive glasses 3D display has been recently practically applied asone of 3D display modes. According to the 3D display, a phase differenceplate is mounted on a panel of the liquid crystal display. As the phasedifference plate, an examination has been made for a patterned phasedifference plate prepared by aligning the polymerizable liquid crystalcompound to the liquid crystal alignment film to which the alignmenttreatment is applied by the photoalignment method. Patterning of thephase difference plate is performed by irradiating a film with polarizedultraviolet light having a different polarization direction to preparethe liquid crystal alignment film, and then applying polymerizableliquid crystals to the film to allow patterning alignment. Uponpreparing the patterned phase difference plate, time of exposure topolarized ultraviolet light can influence productivity in a process, butthe productivity tends to be further increased as the time of exposurethereto is shorter. Accordingly, in order to shorten the time ofexposure to polarized ultraviolet light, an improvement in sensitivityof the photoalignment film to light has been required.

Moreover, a plastic such as triacetyl cellulose (TAC) and a cyclicolefinic polymer may be occasionally used for the substrate for thephase difference plate. Such a plastic including TAC has a lower heatresistance, as compared with glass. Therefore, when polyimide isobtained by applying a solution containing polyamic acid and a highboiling point solvent onto the substrate of the plastic and heating thesubstrate at a high temperature, use of the resultant polyimide as theliquid crystal alignment film has been difficult in some cases.Furthermore, TAC has a low solvent resistance. Therefore, a solvent thatcan be used is limited according to the method by which the film isprepared by applying an aligning agent to be the liquid crystalalignment film onto the substrate. For example, polyamic acid that hasbeen used for forming polyimide so far has a low solubility in thesolvent that can be applied to TAC, which has been a problem.

CITATION LIST Patent Literature

-   Patent literature No. 1: JP 2947350B.-   Patent literature No. 2: JP 2940354B.-   Patent literature No. 3: WO 2011/115079 A.-   Patent literature No. 4: JP 2005-275364 A.-   Patent literature No. 5: JP 4011652B.-   Patent literature No. 6: JP 2000-212310 A.

SUMMARY OF INVENTION Technical Problem

An object of the invention is to provide a photoalignable polymercomposition that can be aligned even when exposure time is short, andcan be dissolved into a solvent applicable to various substrates, and toprovide a photoalignment film, typically, a liquid crystal alignmentfilm that is prepared using the polymer composition, and is excellent insolvent resistance, transparency and adhesion, and has a highphotoalignment ability to polymerizable liquid crystals.

Solution to Problem

The present inventors have diligently continued to conduct research anddevelopment, as a result, have found that the problem described abovecan be solved by a photoalignable polymer composition containing aspecific photoalignable polymer having a polar group and aphotoalignable group, and a polymer having a group being reactive withthe polar group.

The invention concerns a photoalignable polymer composition, containingas a first component a photoalignable polymer having at least onephotoalignable group and at least one polar group selected from ahydroxyl group and a carboxyl group and having none of a group that isreactive with the polar group, and as a second component a polymerhaving a group that is reactive with the polar group.

The invention also concerns a liquid crystal alignment film formed ofthe photoalignable polymer composition.

The invention further concerns an optical device having a phasedifference plate prepared using the photoalignable polymer composition.

The invention still further concerns a patterned phase difference plateprepared from the photoalignable polymer composition according.

More specifically, the invention is as described below.

Item 1. A photoalignable polymer composition, containing as a firstcomponent a photoalignable polymer having at least one photoalignablegroup and at least one polar group selected from a hydroxyl group and acarboxyl group and having none of a group that is reactive with thepolar group, and as a second component a polymer having a group that isreactive with the polar group.

Item 2. The photoalignable polymer composition according to item 1,wherein the polymer of the second component further has a photoalignablegroup.

Item 3. The photoalignable polymer composition according to item 1 or 2,wherein the photoalignable group included in the photoalignable polymerof the first component is a functional group having a photodimerizableor photoisomerizable structure.

Item 4. The photoalignable polymer composition according to any one ofitems 1 to 3, wherein the photoalignable group included in thephotoalignable polymer of the first component has at least one kind ofstructures represented by formulas (I-1) to (I-3) below:

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 5 carbons in which arbitrary hydrogen may be replaced byfluorine, m represents 2, 4 or 6, and arbitrary hydrogen of a phenylenegroup may be replaced by fluorine, a methyl group or a methoxy group.

Item 5. The photoalignable polymer composition according to any one ofitems 1 to 4, wherein the group that is included in the polymer of thesecond component and reacts with at least one polar group selected fromthe hydroxyl group and the carboxyl group is at least one group selectedfrom an alkoxysilane group, an isocyanate group, a[1′-methylpropylideneamino]carboxyamino group, a (3,5-dimethylpyrazolyl)carbonylamino group and an epoxy group.

Item 6. The photoalignable polymer composition according to item 5,wherein the group that is included in the polymer of the secondcomponent and reacts with at least one polar group selected from thehydroxyl group and the carboxyl group is an alkoxysilane group.

Item 7. The photoalignable polymer composition according to item 6,wherein the polymer of the second component includes at least one kindof constitutional unit represented by formula (II-1-1) below:

wherein, in the formulas, R³ represents hydrogen, an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine,or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogenmay be replaced by fluorine, R² each independently represents hydrogen,an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.

Item 8. The photoalignable polymer composition according to item 5,wherein the group that is included in the polymer of the secondcomponent and reacts with at least one polar group selected from thehydroxyl group and the carboxyl group is at least one group selectedfrom an isocyanate group, a [1′-methylpropylideneamino]carboxyaminogroup and a (3,5-dimethylpyrazolyl)carbonylamino group.

Item 9. The photoalignable polymer composition according to item 8,wherein the polymer of the second component includes at least one kindof constitutional unit represented by formulas (II-2-1) and (II-3-1)below:

wherein, in the formulas, R³ represents hydrogen, an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorineor an alkoxy group having 1 to 20 carbons in which arbitrary hydrogenmay be replaced by fluorine, L represents —CH₂CH₂— or —CH₂CH₂OCH₂CH₂—,R⁶ represents a group represented by formula (II-3-1-1) or (II-3-1-2)below, and z is a mole fraction and satisfies a relationship of z≦1.

Item 10. The photoalignable polymer composition according to item 5,wherein the group that is included in the polymer of the secondcomponent and reacts with at least one polar group selected from thehydroxyl group and the carboxyl group is at least one group selectedfrom an epoxy group.

Item 11. The photoalignable polymer composition according to item 10,wherein the polymer of the second component includes at least one kindof constitutional unit represented by formula (II-4-1) below:

wherein, in the formulas, R³ represents hydrogen, an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorineor an alkoxy group having 1 to 20 carbons in which arbitrary hydrogenmay be replaced by fluorine, T represents a methylene group having 1 to20 carbons in which oxygen may be substituted for arbitrary carbon(however, oxygen is not substituted for adjacent carbonssimultaneously), S represents a group represented by formula (II-4-1-1),(II-4-1-2) or (II-4-1-3), R⁸ represents a methyl group or an ethylgroup, and w represents a mole fraction.

Item 12. The photoalignable polymer composition according to any one ofitems 1 to 11, wherein the photoalignable polymer of the first componentincludes a constitutional unit derived from a monomer having aphotoalignable group, and a constitutional unit derived from at leastone kind of monomer selected from the group of acrylic acid, methacrylicacid, hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to6 carbons, carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and a phenolic hydroxyl group-containing(meth)acrylate.

Item 13. The photoalignable polymer composition according to item 12,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formulas (I-1-1) to(I-3-1) below, and at least one kind of constitutional unit derived fromhydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6carbons.

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —OCO—, represents an integer from 2 to 10, p represents an integerfrom 0 to 2, r represents 0 or 1, y¹, y² and y³ represent a molefraction and satisfy a relationship (0<y¹+y²+y³<1), and arbitraryhydrogen of a phenylene group may be replaced by fluorine, a methylgroup or a methoxy group.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

Item 14. The photoalignable polymer composition according to item 12,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formulas (I-1-1) to(I-3-1) below, and a constitutional unit derived from at least one kindof monomer selected from carboxyl group-containing (meth)acrylate,carboxyl group-containing itaconate and phenolic hydroxylgroup-containing (meth)acrylate.

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —OCO—, is an integer from 2 to 10, p is an integer from 0 to 2, rrepresents 0 or 1, y¹, y² and y³ are a mole fraction and satisfy arelationship (0<y¹+y²+y³<1), and arbitrary hydrogen of a phenylene groupmay be replaced by fluorine, a methyl group or a methoxy group.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

Item 15. The photoalignable polymer composition according to item 13,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formula (I-1-1)below, and a constitutional unit derived from hydroxyalkyl(meth)acrylatehaving a hydroxyalkyl group having 2 to 6 carbons, and the polymer ofthe second component includes a constitutional unit represented byformula (II-1-1) below:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, ora group represented by formula (I-4) below, R⁷ represents hydrogen, analkyl group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine or an alkoxy group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine, Z¹ represents a singlebond, —COO— or —OCO—, o represents an integer from 2 to 10, p representsan integer from 0 to 2, r represents 0 or 1, y is a mole fraction(satisfying a relationship: 0<y<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.

Item 16. The photoalignable polymer composition according to item 13,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formula (I-2-1)below, and a constitutional unit derived from hydroxyalkyl(meth)acrylatehaving a hydroxyalkyl group having 2 to 6 carbons, and the polymer ofthe second component includes a constitutional unit represented byformula (II-1-1) below:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, ora group represented by formula (I-4) below, R⁷ represents hydrogen, analkyl group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine or an alkoxy group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine, Z¹ represents a singlebond, —COO— or —OCO—, o represents an integer from 2 to 10, p representsan integer from 0 to 2, r represents 0 or 1, y is a mole fraction(satisfying a relationship: 0<y<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.

Item 17. The photoalignable polymer composition according to item 13,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formula (I-3-1)below, and a constitutional unit derived from hydroxyalkyl(meth)acrylatehaving a hydroxyalkyl group having 2 to 6 carbons, and the polymer ofthe second component includes a constitutional unit represented byformula (II-1-1) below:

wherein, in the formula, R¹ represents hydrogen or an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine,R³ represents hydrogen, an alkyl group having 1 to 5 carbons in whicharbitrary hydrogen may be replaced by fluorine, or a group representedby formula (I-4) below, Z¹ represents a single bond, —COO— or —OCO—, orepresents an integer from 2 to 10, p represents an integer from 0 to 2,r represents 0 or 1, y is a mole fraction (satisfying a relationship:0<y<1), and arbitrary hydrogen of a phenylene group may be replaced byfluorine, a methyl group or a methoxy group.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.

Item 18. The photoalignable polymer composition according to item 14,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formula (I-1-1)below, and a constitutional unit derived from at least one kind ofmonomer selected from carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and phenolic hydroxyl group-containing(meth)acrylate, and the polymer of the second component includes aconstitutional unit represented by formula (II-1-1) below:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, ora group represented by formula (I-4) below, R⁷ represents hydrogen, analkyl group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine or an alkoxy group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine, Z′ represents a singlebond, —COO— or —OCO—, o represents an integer from 2 to 10, p representsan integer from 0 to 2, r represents 0 or 1, y is a mole fraction(satisfying a relationship: 0<y<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.

Item 19. The photoalignable polymer composition according to item 14,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formula (I-2-1)below, and a constitutional unit derived from at least one kind ofmonomer selected from carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and phenolic hydroxyl group-containing(meth)acrylate, and the polymer of the second component includes aconstitutional unit represented by formula (II-1-1) below:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, ora group represented by formula (I-4) below, R⁷ represents hydrogen, analkyl group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine or an alkoxy group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine, Z¹ represents a singlebond, —COO— or —COO—, o represents an integer from 2 to 10, p representsan integer from 0 to 2, r represents 0 or 1, y is a mole fraction(satisfying a relationship: 0<y<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.

Item 20. The photoalignable polymer composition according to item 14,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formula (I-3-1)below, and a constitutional unit derived from at least one kind ofmonomer selected from carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and phenolic hydroxyl group-containing(meth)acrylate, and the polymer of the second component includes aconstitutional unit represented by formula (II-1-1) below:

wherein, in the formula, R¹ represents hydrogen or an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine,R³ represents hydrogen, an alkyl group having 1 to 5 carbons in whicharbitrary hydrogen may be replaced by fluorine, or a group representedby formula (I-4) below, Z¹ represents a single bond, —COO— or —COO—,represents an integer from 2 to 10, p represents an integer from 0 to 2,r represents 0 or 1, y is a mole fraction (satisfying a relationship:0<y<1), and arbitrary hydrogen of a phenylene group may be replaced byfluorine, a methyl group or a methoxy group.

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.

Item 21. The photoalignable polymer composition according to item 13,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formulas (I-1-1) to(I-3-1) below, and a constitutional unit derived fromhydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6carbons, and the polymer of the second component includes aconstitutional unit represented by formula (II-2-1) or (II-3-1):

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —OCO—, is an integer from 2 to 10, p is an integer from 0 to 2, rrepresents 0 or 1, y¹, y² and y³ are a mole fraction and satisfy arelationship (0<y¹+y²+y³<1), and arbitrary hydrogen of a phenylene groupmay be replaced by fluorine, a methyl group or a methoxy group:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, L represents —CH₂CH₂— or —CH₂CH₂OCH₂CH₂—, R⁶represents a group represented by formula (II-3-1-1) or (II-3-1-2), andz represents a mole fraction:

Item 22. The photoalignable polymer composition according to item 14,wherein the photoalignable polymer of the first component includes atleast one kind of constitutional unit represented by formulas (I-1-1) to(I-3-1) below, and a constitutional unit derived from at least one kindof monomer selected from carboxyl group-containing (meth)acrylate,carboxyl group-containing itaconate and phenolic hydroxylgroup-containing (meth)acrylate, and the polymer of the second componentincludes a constitutional unit represented by formula (II-4-1) below:

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —COO—, o is an integer from 2 to 10, p is an integer from 0 to 2, rrepresents 0 or 1, y² and y³ are a mole fraction and satisfy arelationship (0<y¹+y²+y³<1), and arbitrary hydrogen of a phenylene groupmay be replaced by fluorine, a methyl group or a methoxy group:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1.

wherein, in the formulas, R³ represents hydrogen, an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorineor an alkoxy group having 1 to 20 carbons in which arbitrary hydrogenmay be replaced by fluorine, T represents a methylene group having 1 to20 carbons in which oxygen may be substituted for arbitrary carbon(however, oxygen is not substituted for adjacent carbonssimultaneously), S represents a group represented by formula (II-4-1-1),(II-4-1-2) or (II-4-1-3), R⁸ represents a methyl group or an ethylgroup, and w represents a mole fraction.

Item 23. The photoalignable polymer composition according to any one ofitems 1 to 22, wherein a ratio of the first component is in the range of50.00 to 99.99% by mass and a ratio of the second component is in therange of 0.01 to 50.00% by mass, based on the total mass of the firstcomponent and the second component.

Item 24. The photoalignable polymer composition according to any one ofitems 1 to 22, wherein a ratio of the first component is in the range of70.00 to 99.50% by mass and a ratio of the second component is in therange of 0.50 to 30.00% by mass, based on the total mass of the firstcomponent and the second component.

Item 25. The photoalignable polymer composition according to any one ofitems 1 to 24, containing at least one kind of material selected from asensitizer and a crosslinking agent in the range of 1 to 50% by massbased on the total mass of the first component and the second component.

Item 26. The photoalignable polymer composition according to any one ofitems 1 to 25, containing at least one kind of material selected from anacid compound, a thermal acid generator, and a photoacid generator inthe range of 0.01 to 50% by mass based on the total mass of the firstcomponent and the second component.

Item 27. The photoalignable polymer composition according to any one ofitems 1 to 26, further containing a glycol solvent or a glycol estersolvent that can dissolve the first component and the second component.

Item 28. A liquid crystal alignment film formed of the photoalignablepolymer composition according to any one of items 1 to 27.

Item 29. An optical device having a phase difference plate preparedusing the photoalignable polymer composition according to any one ofitems 1 to 27.

Item 30. A patterned phase difference plate prepared from thephotoalignable polymer composition according to any one of items 1 to27.

Advantageous Effects of Invention

A photoalignable polymer composition of the invention contains aspecific photoalignable polymer having a polar group and aphotoalignable group, and a polymer having a group that is reactive withthe polar group. Therefore, a photoalignable film obtained by applying aphotoaligning agent including the composition to a base material or thelike to allow drying has an excellent sensitivity to allowphotoalignment even with exposure in a short period of time.Furthermore, a liquid crystal alignment film is prepared by aphotoalignment method. Therefore, a complicated treatment process is notrequired, and neither dust nor static electricity is subsequentlygenerated, while the complicated process and generation of dust andstatic electricity are seen in rubbing treatment that has been appliedso far. Therefore, a liquid crystal alignment film having a high opticaluniformity without an alignment defect can be prepared. Thus, a phasedifference plate manufactured using the liquid crystal alignment filmcan keep a high alignment stability.

DESCRIPTION OF EMBODIMENTS

The invention will be explained in detail.

A photoalignable polymer composition of the invention is characterizedby containing as a first component a photoalignable polymer having aphotoalignable group and at least one polar group selected from ahydroxyl group and a carboxyl group, and having none of a group that isreactive with the polar group, and as a second component a polymerhaving a group that is reactive with the polar group. Here, thecomposition may have both the photoalignable group and the polar groupin an identical polymer in some cases.

The photoalignable polymer contained as the first component means apolymer in which a change of a molecular structure in the polymer canoccur to cause anisotropy by irradiation with light, for example, planepolarized light, typically, a polymer in which at least onephotoreaction selected from a photoisomerization reaction, aphotodimerization reaction and a photolytic reaction is caused byirradiation with light, for example, plane polarized light. Moreover,the photoalignable group means a group in which a change of a molecularstructure in the group can occur by irradiation with light, for example,plane polarized light, typically, a group in which at least onephotoreaction selected from a photoisomerization reaction, aphotodimerization reaction and a photolytic reaction is caused byirradiation with light, for example, plane polarized light. Among thephotoalignable groups, a group in which the photoisomerization reactionis caused and a group in which the photodimerization reaction is causedare preferred, and the group in which the photodimerization reaction iscaused is further preferred.

The photoisomerization reaction means a reaction that causes stericisomerization or structural isomerization by action of light. Examplesof materials in which the photoisomerization reaction is caused areknown, such as a material having a cinnamic acid skeleton (K. Ichimuraet al., Macromolecules, 30, 903 (1997)), a material having an azobenzeneskeleton (K. Ichimura et al., Mol. Cryst. Liq. Cryst., 298, 221 (1997)),a material having a hydrazono-β-ketoester skeleton (S. Yamamura et al.,Liquid Crystals, Vol. 13, No. 2, page 189 (1993)), a material having astilbene skeleton (J. G. Victor and J. M. Torkelson, Macromolecules, 20,2241 (1987)), and a material having a spiropyran skeleton (K. Ichimuraet al., Chemistry Letters, page 1063 (1992); K. Ichimura et al., ThinSolid Films, Vol. 235, page 101 (1993)).

As the group in which the photoisomerization reaction is caused, a groupthat includes a C═C bond or N═N bond and undergoes thephotoisomerization reaction is preferred. Specific examples of such agroup include a group having a cinnamic acid skeleton, a group having anazobenzene skeleton, a group having a hydrazono-β-ketoester skeleton, agroup having a stilbene skeleton, and a group having a spiropyranskeleton. The groups may be included in a polymer main chain or sidechain.

The photodimerization reaction means a reaction in which an additionreaction occurs between two groups by action of light, and typically, aring structure is formed. Examples of materials in which thephotodimerization is caused known, such as a material having a cinnamicacid skeleton (M. Schadt et al., J. Appl. Phys., Vol. 31, No. 7, page2155 (1992), a material having a coumarin skeleton (M. Schadt et al.,Nature., Vol. 381, page 212 (1996)), a material having a chalconeskeleton (Toshihiro Ogawa et al., Preprints of Symposium on LiquidCrystals (Ekisho Toronkai Koen Yokoshu in Japanese), 2AB03 (1997)), anda material having a benzophenone skeleton (Y. K. Jang et al., SID Int.Symposium Digest, P-53 (1997)).

Specific examples of the groups in which the photodimerization reactionis caused include a group having a cinnamic acid skeleton, a grouphaving a coumarin skeleton, a group having a chalcone skeleton, and agroup having a benzophenone skeleton. Among the groups, a group having acinnamic acid skeleton or a group having a coumarin skeleton ispreferred, and a group having a cinnamic acid skeleton is furtherpreferred.

The groups may be included in the polymer main chain or side chain, butis preferably included in the side chain.

Specific examples of the groups having the cinnamic acid skeletoninclude a group having at least one kind of structure represented bygeneral formulas (I-1) to (I-3) below.

wherein, R¹ represents hydrogen or an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, preferably, amethyl group. Then, m represents an integer from 2 to 10, and m informula (I-1) preferably represents 2, 4 or 6. Moreover, arbitraryhydrogen of a phenylene group included in the formulas may be replacedby fluorine, a methyl group or a methoxy group. Among the groupsrepresented by the formulas (I-1) to (I-3), a group represented byformula (I-3) is preferred.

In order to introduce the groups represented by formulas (I-1) to (I-3)into the photoalignable polymer forming the first component, forexample, at least one of photoalignable polymer monomer forming aconstitutional unit represented by formulas (I-1-1), (I-2-1) and (I-3-1)may be polymerized.

In the formulas, a parenthesized moiety subscribed with y¹, y² or y³represents a moiety to be included in the polymer main chain, and y² andy³ represent a mole fraction (0<y¹+y²+y³<1) of the constitutional unitincluded in the photoalignable polymer. In the formulas, R¹ representshydrogen or an alkyl group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, R³ represents hydrogen, an alkylgroup having 1 to 5 carbons in which arbitrary hydrogen may be replacedby fluorine, or a group represented by formula (I-4) below, R⁷represents hydrogen, an alkyl group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine or an alkoxy group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine,Z¹ represents a single bond, —COO— or —OCO—, represents an integer from2 to 10, p represents an integer from 0 to 2, and r represents 0 or 1.Arbitrary hydrogen of a phenylene group included in the formulas may bereplaced by fluorine, a methyl group or a methoxy group.

In the formula, R⁹ represents hydrogen or a methyl group, and grepresents 0 or 1.

Content of the constitutional unit (typically the constitutional unitsrepresented by formulas (I-1-1), (I-2-1) and (I-3-1)) derived from themonomer having the photoalignable group is ordinarily in the range ofapproximately 5% by mass to approximately 99.99% by mass, preferably, inthe range of approximately 20 to approximately 95.0% by mass, furtherpreferably, in the range of approximately 30 to approximately 90% bymass, based on the total mass of the photoalignable polymer forming thefirst component.

Specific examples of the photoalignable polymer monomer forming theconstitutional unit represented by formula (I-1-1) include monomersrepresented by formulas (I-1-1-a) to (I-1-1-1) and formulas (I-1-1-m) to(I-1-1-x) below (in the formulas, R⁹ represents hydrogen or a methylgroup, and R¹⁰ represents an alkyl group having 1 to 20 carbons).

Specific examples of the photoalignable monomer forming theconstitutional unit represented by formula (I-2-1) include monomersrepresented by formulas (I-2-1-a) to (I-2-1-1) and formulas (I-2-1-m) to(I-2-1-x) below (in the formulas, R⁹ represents hydrogen or a methylgroup, and R¹⁰ represents an alkyl group having 1 to 20 carbons).

Specific examples of the photoalignable monomer forming theconstitutional unit represented by formula (I-3-1) include monomersrepresented by formulas (I-3-1-a) to (I-3-1-i) and formulas (I-3-1-j) to(I-3-1-r) below (in the formulas, R⁹ represents hydrogen or a methylgroup, and R¹⁰ represents an alkyl group having 1 to 20 carbons).

Among the monomers, a photoalignable monomer forming the constitutionalunit represented by formula (I-3-1) described above is preferred, and aphotoalignable monomer represented by formula (I-3-1) described above,wherein R⁶ is a methyl group, and equations: o=2 and p=0 are satisfied,and R¹ is a methyl group is further preferred. The photoalignablepolymer monomers may be used alone in one kind or in combination withtwo or more kinds.

The photoalignable polymer forming the first component is characterizedby further having at least one polar group selected from a hydroxylgroup and a carboxyl group. When the polar groups are included in thephotoalignable polymer, adhesion, with the substrate or the like, of thephotoalignable polymer composition containing the photoalignable polymercan be improved, and also a reaction with the polymer being the secondcomponent as described later is allowed, and thus alignment sensitivityof the photoalignable polymer composition obtained to light is improved.In addition, the hydroxy group includes both an alcoholic hydroxyl groupand a phenolic hydroxyl group.

In order to introduce the hydroxyl group or the carboxyl group into thephotoalignable polymer, for example, a constitutional unit derived froma monomer having a hydroxyl group or a monomer having a carboxyl groupmay be included into the photoalignable polymer, and specifically, amonomer mixture containing the photoalignable monomer and a monomerhaving a hydroxyl group or a monomer having a carboxyl group may bepolymerized.

Specific examples of the monomers having the hydroxyl group includehydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6carbons (alcoholic hydroxyl group-containing (meth)acrylate) such as2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate,4-hydroxybutyl(meth)acrylate, 5-hydroxypentyl(meth)acrylate and6-hydroxyhexyl(meth)acrylate; and phenolic hydroxyl group-containing(meth)acrylate such as 4-hydroxyphenoxy(meth)acrylate,2-(4-hydroxyphenoxy) ethyl(meth)acrylate,3-(4-hydroxyphenoxy)propyl(meth)acrylate,4-(4-hydroxyphenoxy)butyl(meth)acrylate, 5-(4-hydroxyphenoxy)pentyl(meth)acrylate and 6-(4-hydroxyphenoxy) hexyl(meth)acrylate. Amongthe monomers having the hydroxyl group, 2-hydroxyethyl(meth)acrylate,4-hydroxyphenoxy(meth)acrylate or the like is preferred. The monomershaving the hydroxyl group may be used alone in one kind or incombination with two or more kinds. In addition, (meth)acrylate hereinmeans a generic term for acrylate and methacrylate, and (meth)acrylatemeans a generic term for acrylate and methacrylate.

Specific examples of the monomers having the carboxyl group includecarboxyl group-containing (meth)acrylate such asω-carboxypolycaprolactone mono(meth)acrylate, mono hyrdoxyethylphthalate(meth)acrylate, mono[2-((meth)acryloxy)ethyl]succinate, andmono[2-((meth)acryloxy)ethyl]maleate; carboxyl group-containingitaconate such as methyl itaconate, ethyl itaconate, propyl itaconate,isopropyl itaconate and butyl itaconate; and methacrylic acid andacrylic acid. Among the monomers having the carboxyl group, acrylicacid, methacrylic acid, methyl itaconate or the like is preferred. Themonomers having the carboxyl group may be used alone in one kind or incombination with two or more kinds. Moreover, the monomer having thehydroxyl group and the monomer having the carboxyl group may be mixedand used. In addition, (meth)acryloxy herein means a generic term foracryloxy and methacryloxy.

Content of the constitutional unit derived from the monomer having atleast one polar group selected from the hydroxyl group and the carboxylgroup is ordinarily in the range over approximately 0% by mass, and inthe range of approximately 0.01% by mass to approximately 95% by mass,preferably, in the range of approximately 5 to approximately 80% bymass, further preferably, in the range of approximately 10 toapproximately 60% by mass, based on the total mass of the photoalignablepolymer forming the first component.

The photoalignable polymer being the first component is alsocharacterized by having none of a group that is reactive with at leastone polar group selected from the hydroxyl group and the carboxyl group.When the first component includes no such a group that is reactive withthe polar group, the first component polymers do not undergo a reactionwith each other, and can efficiently react with the second component asdescribed later.

The photoalignable polymer forming the first component preferablyincludes a polymer including at least one kind of constitutional unitrepresented by formula (I-1-1) above, and a constitutional unit derivedfrom hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to6 carbons, a polymer including at least one kind of constitutional unitrepresented by formula (I-2-1) above, and a constitutional unit derivedfrom hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to6 carbons, and a polymer including at least one kind of constitutionalunit represented by formula (I-3-1) above, and a constitutional unitderived from hydroxyalkyl(meth)acrylate having a hydroxyalkyl grouphaving 2 to 6 carbons.

Moreover, the photoalignable polymer forming the first componentpreferably includes a polymer including at least one kind ofconstitutional unit represented by formula (I-1-1) above, and aconstitutional unit derived from at least one kind of monomer selectedfrom carboxyl group-containing (meth)acrylate, carboxyl group-containingitaconate and phenolic hydroxyl group-containing (meth)acrylate, apolymer including at least one kind of constitutional unit representedby formula (I-2-1) above, and a constitutional unit derived from atleast one kind of monomer selected from carboxyl group-containing(meth)acrylate, carboxyl group-containing itaconate and phenolichydroxyl group-containing (meth)acrylate, and a polymer including atleast one kind of constitutional unit represented by formula (I-3-1)above, and a constitutional unit derived from at least one kind ofmonomer selected from carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and phenolic hydroxyl group-containing(meth)acrylate.

The photoalignable polymer forming the first component may include aconstitutional unit having a group other than the photoalignable group,the hydroxyl group and the carboxyl group under the conditions withoutincluding a group that is reactive with at least one polar groupselected from the hydroxyl group and the carboxyl group. In order toincorporate such a constitutional unit into the polymer, for example, amixture containing the photoalignable monomer and the monomer having thehydroxyl group or the monomer having the carboxyl group, and alsocontaining any other monomer without including the group that isreactive with at least one polar group selected from the hydroxyl groupand the carboxyl group may be polymerized.

Specific examples of other monomers described above include alkylmono(meth)acrylate such as methyl(meth)acrylate, ethyl(meth)acrylate,butyl(meth)acrylate and 2-ethylhexyl(meth)acrylate; arylmono(meth)acrylate such as phenyl(meth)acrylate andbenzyl(meth)acrylate; polyfunctional (meth)acrylate having no hydroxylgroup, no carboxyl group and no photoalignable group, such as1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate,diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate,polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylatedtrimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritoltri(meth)acrylate, pentaerythritol tetra(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, dicyclopentanyl di(meth)acrylate, ethoxylatedhydrogenated bisphenol A di(meth)acrylate, ethoxylated bisphenol Adi(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, ethoxylatedbisphenol S di(meth)acrylate, hydroxypropyl di(meth)acrylate, diethyleneglycol bishydroxypropyl(meth)acrylate, and monohydroxypentaerythritoltri(meth)acrylate, acrylamide, methacrylamide and any other vinylmonomer such as vinyl ether, a styrene derivative and vinyl ester.

Moreover, as any other monomer described above, a commercially availablemonofunctional monomer or polyfunctional monomer can also be used.Specific examples include 1,6-hexanediol di(meth)acrylate andpentaerythritol tetra(meth)acrylate.

The monomers may be used alone in one kind, or may be used by mixing twoor more kinds.

Weight average molecular weight of the polymer forming the firstcomponent is not particularly limited, as long as advantageous effectsof the invention are produced, but preferably, approximately 500,000 orless, further preferably, approximately 200,000 or less, preferably,approximately 1,000 or more, further preferably, approximately 5,000 ormore. The weight average molecular weight of the polymer of theinvention is expressed in terms of a value determined as a relativevalue to a standard reference material (standard polystyrene) accordingto a gel permeation chromatograph (GPC).

The photoalignable polymer being the first component may be ahomopolymer of one kind or a mixture of polymers of two or moredifferent kinds.

The polymer contained as the second component is characterized by havingthe group that is reactive with at least one polar group selected fromthe hydroxyl group and the carboxyl group.

Alignment sensitivity of the photoalignable polymer (a polymer includinga group having a cinnamic acid skeleton, for example) being the firstcomponent is easily affected by a structure of the monomer forming thephotoalignable polymer, or a concentration of the photoalignable group,and also various conditions such as conditions upon coating the polymeras a photoalignment film (a film thickness, a baking temperature or asolvent contained in the composition upon coating the polymer). Then,when the alignment sensitivity decreases, an exposure amount (time)required for photoalignment in a manufacture step increases to decreaseproduction efficiency. In a case of the photoalignable polymercomposition of the invention, although a detailed mechanism is unknown,at least one kind of polar group selected from the hydroxyl group andthe carboxyl group included in the first component interacts (typicallyreacts) with the group that is included in the second component and isreactive with the polar group, and thus the alignment sensitivity can bepresumably increased by an effect of shortening a distance betweenadjacent photoalignable groups (distance between double bond partsrelating to photodimerization in a case where the group having thecinnamic acid skeleton performs a photodimerization reaction, forexample). Therefore, even without changing the structure or the contentof the photoalignable group included in the photoalignable polymercomposition, coating conditions, or the like, a photoalignment filmhaving a high sensitivity to light can be presumably prepared. Moreover,when the second component is contained in addition to the firstcomponent, an improvement is allowed in adhesion of the photoalignmentfilm prepared from the polymer composition with the substrate or thepolymerizable liquid crystal film.

Specific examples of the group that is reactive with the polar groupinclude an alkoxysilane group, an isocyanate group, a[1′-methylpropylideneamino]carboxyamino group, a(3,5-dimethylpyrazolyl)carbonylamino group and an epoxy group.

One example of the group including the alkoxysilane group includes agroup represented by formula (II-1) below.

In the formula, R² each independently represents hydrogen, an alkylgroup having 1 to 4 carbons or an alkoxy group having 1 to 4 carbons,and at least one of R² is an alkoxy group having 1 to 4 carbons. Thealkoxy group having 1 to 4 carbons preferably includes a methoxy groupand an ethoxy group. R² described above preferably includes hydrogen, amethyl group, a methoxy group and an ethoxy group. In the formula, qrepresents an integer from 0 to 10, preferably, 2 or 3.

One example of the group including the isocyanate group includes a grouprepresented by formula (II-2) below.

In the formula, L represents —CH₂CH₂— or —CH₂CH₂OCH₂CH₂—.

One example of the group including the[1′-methylpropylideneamino]carboxyamino group includes groupsrepresented by formulas (II-3) and (II-3-1-1) below.

In the formula, L represents —CH₂CH₂— or —CH₂CH₂OCH₂CH₂—, and R⁴represents a group represented by formula (II-3-1-1) above.

One example of the group including (3,5-dimethylpyrazolyl)carbonylaminogroup includes groups represented by formulas (II-3) and (II-3-1-2)below.

In the formula, L represents —CH₂CH₂— or —CH₂CH₂OCH₂CH₂—, and R⁴represents a group represented by formula (II-3-1-2) above.

The epoxy group includes an oxirane and an oxetane. One example of theoxirane includes groups represented by formulas (II-4) and (II-4-1-1)below, and groups represented by formulas (II-4) and (II-4-1-2) below.

In the formulas, T represents a methylene group having 1 to 20 carbonsin which oxygen may be substituted for arbitrary carbon (however, oxygenis not substituted for adjacent carbons simultaneously), and Srepresents a group represented by formula (II-4-1-1) or (II-4-1-2).

One example of the group including the oxetane includes groupsrepresented by formulas (II-4) and (II-4-1-3) below.

In the formulas, T represents a methylene group having 1 to 20 carbonsin which oxygen may be substituted for arbitrary carbon (however, oxygenis not substituted for adjacent carbons simultaneously), S represents agroup represented by formula (II-4-1-3), and R⁵ represents a methylgroup or an ethyl group.

Among the groups, when reactivity with the hydroxyl group or thecarboxyl group included in the first component is taken intoconsideration, an alkoxysilane group, an isocyanate group, a[1′-methylpropylideneamino]carboxyamino group or a(3,5-dimethylpyrazolyl)carbonylamino group is preferred, and an alkoxygroup or an isocyanate group is further preferred.

When the polar group included in the photoalignable polymer of the firstcomponent is an alcoholic hydroxyl group, among the groups, analkoxysilane group, an isocyanate group, a[1′-methylpropylideneamino]carboxyamino group or a(3,5-dimethylpyrazolyl)carbonylamino group is preferred. Moreover, whenthe polar group included in the photoalignable polymer of the firstcomponent is a carboxyl group or a phenolic hydroxyl group, among thegroups, an alkoxy silane group or an epoxy group is preferred. Among thegroups, when reactivity with the polar group included in the firstcomponent is taken into consideration, an alkoxysilane group, anisocyanate group, a [1′-methylpropylideneamino]carboxyamino group or a(3,5-dimethylpyrazolyl)carbonylamino group is preferred. The groups thatare reactive with the polar group may be contained alone in one kind orin two or more kinds in the polymer of the second component.

In order to introduce the group that is reactive with at least one polargroup selected from the hydroxyl group and the carboxyl group into thepolymer of the second component, for example, the constitutional unitderived from the monomer including the group that is reactive with thepolar group may be incorporated into the photoalignable polymer, andspecifically, a monomer mixture containing the monomer including thegroup that is reactive with the polar group may be polymerized.

Specific examples of the constitutional units derived from the monomerhaving the alkoxysilane group include at least one kind ofconstitutional unit represented by formula (II-1-1) below.

In the formula, a parenthesized moiety subscribed with x represents amoiety to be included in the polymer main chain, and x represents a molefraction (x≦1) of the constitutional unit included in the polymer of thesecond component. In the formula, R³ represents hydrogen, an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, preferably, a methyl group. In theformula, R² each independently represents hydrogen, an alkyl grouphaving 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons, and atleast one of R² is an alkoxy group having 1 to 4 carbons. In theformula, two or more of R² preferably represent a methoxy group. In theformula, q represents an integer from 0 to 10, preferably, represents 3.

The mole fraction x is preferably approximately 0.7 or less, furtherpreferably, approximately 0.5 or less, still further preferably,approximately 0.3 or less. The mole fraction x is preferablyapproximately 0.01 or more, further preferably, approximately 0.1 ormore.

Specific examples of the monomers forming the constitutional unitrepresented by formula (II-1-1) above include monomers represented byformulas (II-1-1a) to (II-1-1j) below.

In the formulas, R¹¹ represents hydrogen or a methyl group, preferably,a methyl group. In the formulas, R¹² represents hydrogen or an alkylgroup having 1 to 4 carbons, preferably, a methyl group. In theformulas, q represents an integer from 0 to 10, preferably, 3. Themonomers having the alkoxysilane group may be used alone in one kind, ormay be used by mixing two or more kinds.

Specific examples of the constitutional units derived from the monomerhaving the isocyanate group includes at least one of constitutional unitrepresented by formula (II-2-1) below. Specific examples of theconstitutional units derived from the monomer having the[1′-methylpropylideneamino]carboxyamino group include at least one ofconstitutional units represented by formulas as described below orformula (II-3-1) and formula (II-3-1-1) below. Specific examples of theconstitutional units derived from the monomer having the(3,5-dimethylpyrazolyl)carbonylamino group include at least one ofconstitutional units represented by formula (II-3-1) and formula(II-3-1-2) below.

In the formulas, a parenthesized moiety subscribed with z represents amoiety to be included in the polymer main chain, and z represents a molefraction (z≦1) of the constitutional unit included in the polymer of thesecond component. In the formulas, R³ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, L represents —CH₂CH₂— or—CH₂CH₂OCH₂CH₂—, and R⁴ represents a group represented by formula(II-3-1-1) or (II-3-1-2) below.

The mole fraction z is preferably approximately 0.7 or less, furtherpreferably, approximately 0.5 or less, still further preferably,approximately 0.3 or less. The mole fraction z is preferablyapproximately 0.01 or more, further preferably, approximately 0.1 ormore.

The monomer having the isocyanate group, the monomer having the[1′-methylpropylideneamino]carboxyamino group, and the monomer havingthe (3,5-dimethylpyrazolyl)carbonylamino group may be used alone in onekind, or may be used by mixing two or more kinds.

Specific examples of the constitutional units derived from the monomerhaving the epoxy group includes at least one of constitutional unitrepresented by formula (II-4-1) and formula (II-4-1-1) below, or formula(II-4-1-2) below. Moreover, specific examples of the constitutionalunits derived from the monomer having the oxetane group include at leastone of constitutional unit represented by formula (II-4-1) and(II-4-1-3) below, respectively.

In the formulas, a parenthesized moiety subscribed with w represents amoiety to be included in the polymer main chain, and w represents a molefraction (w≦1) of the constitutional unit included in the polymer of thesecond component. R³ represents hydrogen, an alkyl group having 1 to 20carbons in which arbitrary hydrogen may be replaced by fluorine or analkoxy group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine. T represents a methylene group having 1 to 20carbons in which oxygen may be substituted for arbitrary carbon(however, oxygen is not substituted for adjacent carbonssimultaneously). S represents a group represented by formula (II-4-1-1),(II-4-1-2) or (II-4-1-3), and R⁸ represents a methyl group or an ethylgroup.

The mole fraction w is preferably approximately 0.7 or less, furtherpreferably, approximately 0.5 or less, still further preferably,approximately 0.3 or less. The mole fraction w preferably isapproximately 0.01 or more, further preferably, approximately 0.1 ormore.

The monomers having the monomer including the epoxy group may be usedalone in one kind, or may be used by mixing two or more kinds.

Content of the constitutional unit derived from the monomer includingthe group that is reactive with at least one polar group selected fromthe hydroxyl group and the carboxyl group (typically, the constitutionalunit represented by the formulas (I-1-1), (I-2-1) and (I-3-1)) isordinarily in the range of approximately 5% by mass to approximately99.99% by mass, preferably, in the range of approximately 20 toapproximately 95% by mass, further preferably, in the range ofapproximately 30 to approximately 90% by mass, based on the total massof the polymer being the second component. When the content of the groupthat is reactive with the polar group is too large, alignmentsensitivity of the photoalignment film prepared from the photoalignablepolymer composition, wettability of the film, or the like mayoccasionally decrease.

According to one preferred embodiment, the photoalignable group isincluded in the polymer being the second component. When thephotoalignable group is included in the polymer being the secondcomponent, sensitivity of the photoalignable group to light in thephotoisomerization reaction, the photodimerization reaction or the liketends to be further improved. Although the detailed mechanism isunknown, the photoalignable group included in the first component andthe photoalignable group included in the second component are presumedto form a positional relationship in which sensitivity of thephotoalignable group to light in the photoisomerization reaction, thephotodimerization reaction or the like is further improved.

Specific examples of the photoalignable groups include groupsrepresented by formulas (I-1) to (I-3) above as exemplified as the firstcomponent above, and among the groups, a group represented by formula(I-3) is preferred. In order to introduce into the groups represented byformulas (I-1) to (I-3) into the polymer forming the second component,for example, a photoalignable monomer forming the constitutional unitrepresented by formulas (I-1-1), (I-2-1) and (I-3-1) above may beincorporated into the monomer mixture forming the second componentabove. The photoalignable monomers may be used alone in one kind, or maybe used by mixing two or more kinds.

Content of the constitutional unit derived from the monomer having thephotoalignable group (typically, the constitutional unit represented bythe formulas (I-1-1), (I-2-1) and (I-3-1)) is preferably in the range ofapproximately 0.01 to approximately 50% by mass, further preferably, inthe range of approximately 0.1 to approximately 30% by mass, based onthe total mass of the polymer forming the second component.

The polymer forming the second component may include a constitutionalunit derived from any other monomer. In order to introduce such aconstitutional unit into the polymer forming the second component, anyother monomer may be incorporated into the monomer mixture forming thesecond component. Specific examples of other monomers that can becontained in the second component include other monomers exemplified inthe first component, such as alkyl mono(meth)acrylate, arylmono(meth)acrylate, polyfunctional (meth)acrylate having no hydroxylgroup, no carboxyl group and no photoalignable group, acrylamide,methacrylamide, and any other vinyl monomer such as vinyl ether, astyrene derivative and vinyl ester. Other monomers as described abovemay be used alone in one kind, or may be used by mixing two or morekinds.

In addition, any other monomer may be further contained in the monomermixture forming the second component within the range in whichadvantageous effects of the invention are not adversely affected.

Weight average molecular weight of the polymer forming the secondcomponent is not particularly limited, as long as advantageous effectsof the invention are produced, but preferably, approximately 500,000 orless, further preferably, approximately 200,000 or less, still furtherpreferably, approximately 100,000 or less, preferably, approximately1,000 or more, further preferably, approximately 5,000 or more.

The photoalignable polymer being the second component may be ahomopolymer of one kind or a mixture of polymers of two or moredifferent kinds.

When the first component is a polymer including at least one ofconstitutional unit selected from formulas (I-1-1), (I-2-1) and (I-3-1)above, and a constitutional unit derived from hydroxyalkyl(meth)acrylatehaving a hydroxyalkyl group having 2 to 6 carbons, the second componentpreferably includes a polymer including a constitutional unitrepresented by formulas (II-1-1), (II-2-1) and (II-3-1) above.

When the first component is a polymer including at least one ofconstitutional unit selected from formula (I-1-1), (I-2-1) and (I-3-1)above, and a constitutional unit derived from at least one kind ofmonomer selected from carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and phenolic hydroxyl group-containing(meth)acrylate, the second component is preferably a polymer includingat least one of constitutional unit selected from formulas (II-1-1) and(II-4-1), further preferably, a polymer including a constitutional unitrepresented by formula (II-1-1) above.

An amount of blending the first component and the second component isnot particularly limited, as long as advantageous effects of theinvention are produced, but ordinarily, a ratio of the first componentis in the range of approximately 50.00 to approximately 99.99% by mass,and a ratio of the second component is in the range of approximately0.01 to approximately 50.00% by mass, further preferably, a ratio of thefirst component is in the range of approximately 70.0 to approximately99.50% by mass, and a ratio of the second component is in the range ofapproximately 0.50 to approximately 30.00% by mass, based on the totalmass of the first component and the second component.

A method for manufacturing the polymers forming the first component andthe second component is not particularly limited, but can bemanufactured by an ordinary method that is industrially applied. Forexample, the polymers can be manufactured by performing cationicpolymerization, radical polymerization, anionic polymerization or thelike of the monomer mixture forming the first component or the secondcomponent. Among the polymerization methods, radical polymerization ispreferred from a viewpoint of ease of reaction control.

As a polymerization initiator for the radical polymerization, variouskinds of polymerization initiators such as a thermal radicalpolymerization initiator and a photoradical polymerization initiator canbe used.

The thermal radical polymerization initiator generates a radical byheating the initiator at a decomposition temperature or higher. Specificexamples of the thermal radical polymerization initiators include ketoneperoxides (methyl ethyl ketone peroxide and cyclohexanon peroxide),diacyl peroxides (acetyl peroxide and benzoyl peroxide), hydroperoxides(hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide),dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide anddilauroyl peroxide), peroxyketals (dibutylperoxy cyclohexane), alkylperesters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate andtert-amyl peroxy-2-ethylcyclohexanoate), persulfates (potassiumpersulfate, sodium persulfate and ammonium persulfate) and an azocompound (azobisisobutyronitril, dimethyl 2,2′-azobisisobutyrate and2,2′-di(2-hydroxyethyl)azobisisobutyronitril). The thermal radicalpolymerization initiators can be used alone in one kind or incombination with two or more kinds.

The photoradical polymerization initiator generates a radical byirradiation with light. Specific examples of the photoradicalpolymerization initiators include benzophenone, Michler's ketone,4,4′-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethyl thioxanthone, 2-ethylanthraquinone, acetophenone,2-hydroxy-2-methylpropiophenone,2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenylketone, isopropyl benzoin ether, isobutyl benzoin ether,2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone,camphorquinone, benzanthrone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, ethyl2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoate,isoamyl-dimethylaminobenzoate,4,4′-di(t-butylperoxycarbonyl)benzophenone,3,4,4′-tri(t-butylperoxycarbonyl)benzophenone,2,4,6-trimethylbenzoyldiphenylphosphine oxide,2-(4′-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(3′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(2′,4′-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(2′-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,2-(4′-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine,4-[p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine,1,3-bis(trichloromethyl)-5-(2′-chlorophenyl)-s-triazine,1,3-bis(trichloromethyl)-5-(4′-methoxyphenyl)-s-triazine,2-(p-dimethylaminostyryl)benzoxazole,2-(p-dimethylaminostyryl)benzthiazole, 2-mercaptobenzothiazole,3,3′-carbonylbis(7-diethylaminocoumarin),2-(o-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,3-(2-methyl-2-dimethylaminopropionyl)carbazole,3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecylcarbazole,1-hydroxycyclohexyl phenyl ketone,bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)-phenyl)titanium,3,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone,3,3′,4,4′-tetra(t-hexylperoxycarbonyl)benzophenone,3,3′-di(methoxycarbonyl)-4,4′-di(t-butylperoxycarbonyl)benzophenone,3,4′-di(methoxycarbonyl)-4,3′-di(t-butylperoxycarbonyl)benzophenone,4,4′-di(methoxycarbonyl)-3,3′-di(t-butylperoxycarbonyl)benzophenone,2-(3-methyl-3H-benzothiazole-2-ylidene)-1-naphthalene-2-yl-ethanone or2-(3-methyl-1,3-benzothiazole-2 (3H)-ylidene)-1-(2-benzoyl)ethanone. Thephotopolymerization initiators can be used alone or in combination withtwo or more kinds.

A form of the radical polymerization is not particularly limited. Theradical polymerization can be performed in various kinds of forms suchas emulsion polymerization, suspension polymerization, dispersionpolymerization, precipitation polymerization, bulk polymerization andsolution polymerization. In addition, with regard to a form ofpolymerization, polymerization methods in the cationic polymerization,the anionic polymerization or the like can also be applied in variouskinds of forms in a similar manner. Other forms are described, forexample, in “Synthesis of Polymers (First Volume) (Kobunshi no Gosei(Jyo) in Japanese), (edited by Takeshi Endo, Kodansha Ltd., issued in2010).

Hereinafter, general solution polymerization as one of the forms ofradical polymerization will be explained. The solution polymerization isa polymerization form in which polymerization is ordinarily performed ina solvent using a polymerization catalyst dissolvable in the solvent.The solvent in the solution polymerization can be appropriately selectedaccording to a monomer or the like to be used. An organic solventordinarily includes an organic compound having a boiling point underatmospheric pressure within the range of approximately 50 toapproximately 200° C., preferably, an organic compound to uniformlydissolve the monomer, and components or the like produced during apolymerization process.

The solvent used in the radical polymerization is not particularlylimited, if the solvent does not adversely affect the radicalpolymerization. Specific examples include:

an aromatic compound such as benzene, toluene, xylene and ethylbenzene;an aliphatic compound such as pentane, hexane, heptane, octane,cyclohexane and cycloheptane;alcohol such as methanol, ethanol, 1-propanol, 2-propanol and ethyleneglycol;ether such as dibutyl ether, ethylene glycol monomethyl ether, ethyleneglycol dimethyl ether, tetrahydrofuran and dioxane;ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone,cyclohexanone and cyclopentanone;ester such as ethyl acetate, butyl acetate, amyl acetate andγ-butyrolactone;a glycol solvent such as ethylene glycol, diethylene glycol, triethyleneglycol and propylene glycol; anda glycol ether solvent such as diethylene glycol monomethyl ether,triethylene glycol monomethyl ether, propylene glycol monomethyl ether,1-methoxy-2-propanol and 3-methoxy-3-methyl-1-butanol. In addition, theorganic solvents can be used alone in one kind or in combination withtwo or more kinds.

From a viewpoint of control of molecular weight, control of molecularweight distribution, polymerization acceleration or the like with regardto the polymer of the first component and the second component, a chaintransfer agent may be used upon performing the radical polymerization.When the chain transfer agent is used, a polymer having a more uniformmolecular weight distribution in a preferred molecular weight range canbe obtained.

Specific examples of the chain transfer agents include: mercaptans suchas β-mercaptopropionic acid, methyl β-mercaptopropionate,isopropylmercaptan, octylmercaptan, decylmercaptan, dodecylmercaptan,tert-dodecylmercaptan, octadecylmercaptan, thiophenol,p-nonylthiophenol, thiosalicylic acid, mercaptoacetic acid and mercapto;

alkyl halide such as carbon tetrachloride, chloroform, butyl chloride,1,1,1-trichloroethane and 1,1,1-tribromooctane; andlow-activity monomers such as α-methylstyrene and α-methylstyrene dimer.The amount of use of the chain transfer agents can be appropriately setup depending on activity of the chain transfer agent, a combination witha monomer, a solvent, a polymerization temperature or the like, but isordinarily in the range of approximately 0.01 mol % to approximately 50mol % based on the total number of moles of monomers to be used.

Polymerization conditions upon performing the solution polymerizationare not particularly limited, either. The polymerization can beperformed, for example, within a temperature range of approximately 50to approximately 200° C. for approximately 10 minutes to approximately20 hours. From a viewpoint of avoiding deactivation of radicals, thepolymerization is preferably performed under an atmosphere of an inertgas such as nitrogen.

In order to accelerate a reaction between the group that is included inthe first component or the second component and is reactive with thepolar group (hydroxyl group, carboxyl group) and the polar groupthereof, the photoalignable polymer composition of the invention mayfurther contain at least one kind selected from an acid compound, athermal acid generator and a photoacid generator. In addition, thethermal acid generator means a compound that generates acid by heatingordinarily at approximately 60° C. or higher, and the photoacidgenerator means a compound that generates acid by irradiation withlight. Moreover, the thermal acid generator also includes a compoundthat generates acid by irradiation with light.

Specific examples of the acid compounds include inorganic acid such asphosphoric acid and hydrochloric acid; sulfonic acid such asp-phenolsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonicacid, pyridinium-p-toluenesulfonic acid, camphorsulfonic acid,5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid,4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, phthalenesulfonicacid and pyridinium-1-naphthalenesulfonic acid, and organic acid such asformic acid. The acid compounds may be used alone in one kind or incombination with two or more kinds.

Specific examples of the thermal acid generators include4-acetoxyphenyldimethylsulfonium hexafluoroarsenate,benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate,4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate,dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate,4-acetoxyphenylbenzylsulfoniumhexafluoroantimonate,3-benzylbenzothiazolium hexafluoroantimonate,2,4,4,6-tetrabromocyclohexadienone, benzene tosylate and 2-nitrobenzyltosylate. The heat acid generators may be used alone in one kind or incombination with two or more kinds.

Specific examples of the photoacid generators includep-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate (CPI-100p:made by San-Apro Ltd.), p-(phenylthio)phenyldiphenylsulfoniumhexafluoroantimonate (CPI-100A: made by San-Apro Ltd.), ap-(phenylthio)phenyldiphenylsulfonium hexafluorophosphate compound(CPI-200K, CPI-210S: made by San-Apro Ltd.);bis(cyclohexylsulfonyl)diazomethane (WPAG-145: made by Wako PureChemical Industries, Ltd.), bis(t-butylsulfonyl)diazomethane (WPAG-170:made by Wako Pure Chemical Industries, Ltd.),bis(p-toluenesulfonyl)diazomethane (WPAG-199: made by Wako Pure ChemicalIndustries, Ltd.), triphenylsulfoniumtrifluoromethane sulfonate(WPAG-281: made by Wako Pure Chemical Industries, Ltd.),diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate (WPAG-336:made by Wako Pure Chemical Industries, Ltd.),diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate (WPAG-367:made by Wako Pure Chemical Industries, Ltd.), bis(alkylphenyl [having 10to 14 carbons]) iodoniumhexafluorophosphate (WPI-113: made by Wako PureChemical Industries, Ltd.); and 4-isobutylphenyl(4-methylphenyl)iodoniumhexafluorophosphate (Irgacure 250: made by BASF Corporation). Thephotoacid generators may be used alone in one kind or in combinationwith two or more kinds or with a photosensitizer.

A whole amount of blending the acid compound, the acid generator and thephotoacid generator is in the range of approximately 0.01 to 50% bymass, preferably, in the range of approximately 0.1 to approximately 30%by mass, based on the total mass of the photoalignable polymercomposition of the invention.

The photoalignable polymer composition of the invention is suitablyapplied onto the substrate, laminated thereon, and used as a liquidcrystal alignment film, for example. Therefore, characteristicsnecessary for an optical film, an optical display device or the like,such as alignment ability, adhesion with the substrate and a polymerizedliquid crystal film, application uniformity, chemical resistance, heatresistance, transmittance and gas barrier properties, may beoccasionally required. Therefore, various kinds of additives may becontained in the photoalignable polymer composition for the purpose ofproviding the composition with the characteristics or the like.

Specific examples of the additives include a polymer dispersing agent,an applicability improver, an adhesion improver, an ultraviolet lightabsorber, an agglomeration inhibitor, an alkali solubility accelerator,a sensitizer and a crosslinking agent.

Specific examples of the polymer dispersing agents include an acrylicpolymer dispersing agent, a styrenic polymer dispersing agent, anethyleneimine polymer dispersing agent and a urethane polymer dispersingagent. Specific examples of the applicability improver include asilicone resin. Specific examples of the adhesion improver include asilane coupling agent. Specific examples of the ultraviolet lightabsorber include alkoxy benzophenones. Specific examples of theagglomeration inhibitor include sodium polyacrylate. Specific examplesof the alkali solubility accelerator include organic carboxylic acid.

As the sensitizer, a colorless sensitizer and a triplet sensitizer arepreferred. Specific examples of the photosensitizers include an aromaticnitro compound, coumarin (7-diethylamino-4-methylcoumarin,7-hydroxy-4-methylcoumarin, ketocoumarin and carbonylbiscoumarin),aromatic 2-hydroxyketone, and amino-substituted, aromatic2-hydroxyketone (2-hydroxybenzophenone, or mono- ordi-p-(dimethylamino)-2-hydroxybenzophenone), acetophenone,anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline(2-benzoylmethylene-3-methyl-β-naphthothiazoline,2-(β-naphthoylmethylene)-3-methylbenzothiazoline,2-(α-naphthoylmethylene)-3-methylbenzothiazoline,2-(4-biphenoylmethylene)-3-methylbenzothiazoline,2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline,2-(4-biphenoylmethylene)-3-methyl-β-naphthothiazoline,2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthothiazoline), oxazoline(2-benzoylmethylene-3-methyl-β-naphthoxazoline,2-(β-naphthoylmethylene)-3-methylbenzoxazoline,2-(α-naphthoylmethylene)-3-methylbenzoxazoline,2-(4-biphenoylmethylene)-3-methylbenzoxazoline,2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline,2-(4-biphenoylmethylene)-3-methyl-(β-naphthoxazoline,2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthoxazoline), benzothiazole,nitroaniline (m- or p-nitroaniline and 2,4,6-trinitroaniline) ornitroacenaphthene (5-nitroacenaphthene),(2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether,N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone),naphthalene (2-naphthalene methanol, 2-naphthalene carboxylic acid),anthracene (9-anthracene methanol, 9,10-dipropoxyanthracene,9,10-dibutoxyanthracene and 9-anthracene carboxylic acid), benzopyran,azoindolizine and furocoumarin. Among the photosensitizers, aromatic2-hydroxyketone (benzophenone), coumarin, ketocoumarin,carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthoneand acetophenone ketal are preferred.

Specific examples of the crosslinking agents include an oxiranecompound, a melamine compound, an epoxy compound, an isocyanatecompound, a glycoluril compound and a bisazide compound.

An amount of adding the various kinds of additives is appropriatelydetermined depending on an application, the characteristics or the like,but is ordinarily in the range of approximately 0.01 to approximately50% by mass, preferably, in the range of approximately 0.01 toapproximately 30% by mass, based on the total mass of the firstcomponent and the second component. In addition, an amount of adding thesensitizer and the crosslinking agent is ordinarily in the range ofapproximately 0.01 to approximately 50% by mass based on the total massof the first component and the second component.

As the additives, a coupling agent, a surfactant or the like can also beused in addition thereto.

The coupling agent is used in order to improve the adhesion with thesubstrate. Specific examples of the coupling agents include a silanecoupling agent such as 3-glycidoxypropyldimethylethoxysilane,3-glycidoxypropylmethyldiethoxysilane and3-glycidoxypropyltrimethoxysilane; an aluminum coupling agent such asacetoalkoxyaluminum diisopropylate; and a titanate coupling agent suchas tetraisopropylbis(dioctylphosphite)titanate. An amount of adding thecoupling agent is ordinarily approximately 10 parts by mass or lessbased on 100 parts by mass of the components (solid) excluding thesolvent contained in the photoalignable polymer composition.

The surfactant is used in order to improve wettability to a basesubstrate, levelability and applicability thereto. Specific examples ofthe surfactants include a fluorine surfactant such as MEGAFAC F-555,MEGAFAC F-556, MEGAFAC F-557, MEGAFAC F-558, MEGAFAC F-559 and MEGAFACF-561 as made by DIC, Inc.; a silicone surfactant such as Byk-300,Byk-306, Byk-335, Byk-310, Byk-341, Byk-344 and Byk-370 as made byBYK-Chemie GmbH; an acrylic surfactant such as Byk-354, Byk-358 andByk-361 as made by BYK-Chemie GmbH; and a fluorine surfactant such asSC-101 made by Asahi Glass Co., Ltd., and EF-351 and EF-352 as made byTohchem Products Corporation. An amount of adding the surfactant isordinarily in the range of approximately 0.01 to approximately 1 part bymass based on 100 parts by mass of the photoalignable polymercomposition.

The photoalignable polymer composition of the invention may furthercontain a solvent in order to apply the composition, for example, as aphotoaligning agent, to the base material. Such a solvent preferably candissolve the first component and the second component. Specific examplesof the solvent include a glycol solvent such as ethylene glycol,diethylene glycol, triethylene glycol and propylene glycol; a glycolether solvent such as diethylene glycol monomethyl ether, triethyleneglycol monomethyl ether, propylene glycol monomethyl ether,1-methoxy-2-propanol, 2-ethoxyethanol, 3-propoxyethanol and3-methoxy-3-methyl-1-butanol, a glycol ester solvent such as propyleneglycol-1-monomethyl ether acetate, a ketone solvent such ascyclopentanone, cyclohexanone, methyl ethyl ketone and methyl isobutylketone, an aromatic hydrocarbon solvent such as toluene, p-cymene andlimonene, and a cycloalkane solvent such as cyclohexane. When the glycolether solvent is used among the solvents, even if the composition isapplied as the photoaligning agent or the like to a substrate formed oftriacetyl cellulose (TAC), the solvent does not tend to corrode thesubstrate. Furthermore, in order to improve the adhesion with thesubstrate, a mixed solvent prepared by adding a 2-ethoxyethanol solventto the glycol ether solvent such as 1-methoxy-2-propanol may beoccasionally used or the ketone solvent such as cyclopentanone,cyclohexanone and methyl isobutyl ketone may be occasionally mixed withthe glycol ether solvent such as 1-methoxy-2-propanol. An amount to bemixed is in the range of approximately 1 to approximately 50% by mass,preferably, in the range of approximately 5 to approximately 30% bymass, further preferably, in the range of approximately 10 toapproximately 25% by mass, based on the glycol ether solvent. Moreover,several kinds of solvents may be occasionally mixed in order touniformize a film surface during film formation. Specific examplesinclude a mixed solvent of a ketone solvent, an aromatic hydrocarbonsolvent and a cycloalkane solvent, and a mixed solvent of a glycol ethersolvent and an aromatic hydrocarbon solvent. The solvent to be used mayoccasionally influence solubility of a photoalignment film polymer,adhesion with the substrate, film surface uniformity during filmformation, and sensitivity of alignment of polymerizable liquid crystalsduring preparation of a phase difference film. Use of a solvent tosatisfy the characteristics is required.

An amount of adding the solvent is ordinarily in the range ofapproximately 70 to approximately 99 parts by mass based 100 parts bymass of a total of the first component and the second component.

The photoalignment film can be obtained by applying the photoalignablepolymer composition containing the solvent onto the base material or thelike, removing the solvent to obtain a laminated film, and thenirradiating the film with light such as polarized light. Application tothe base material or the like can be performed according to a publiclyknown method such as a spin coating method, a gravure coater method, areverse gravure method, a Mayer bar coater method, a die coater method,a reverse roll coater method, a fountain reverse roll coater method, akiss roll coater method, a bar coater method, a knife coater method, alip coater method and a resist coater method.

After the laminated film is obtained by removing the solvent after theapplication as described above, the film is irradiated with light suchas polarized light. Irradiation with light is preferably performed froma single direction to the film. Molecules in the photoalignable groupincluded in the photoalignable polymer included in the film are alignedby the irradiation with light, and a photoalignment function and opticalanisotropy are developed. Therefore, the photoalignment film can besuitably used as the liquid crystal alignment film.

Specific examples of light applied to the irradiation include X-rays, anelectron beam, ultraviolet light, visible light and infrared light (heatrays). Among the types of light, ultraviolet light is preferred.Wavelength of ultraviolet light is preferably approximately 400nanometers or less, further preferably, in the range of approximately180 to approximately 360 nanometers. As a light source, a low-pressuremercury lamp, a high-pressure mercury lamp, an ultra-high-pressuremercury lamp, a high-pressure discharge lamp, a short arc discharge lampor the like is preferred.

As long as an alignment function can be provided, irradiation with lightmay be performed using unpolarized light, but preferably is performedusing linearly polarized light. Irradiance is preferably in the range ofapproximately 5 mJ/cm² to approximately 2,000 mJ/cm², furtherpreferably, in the range of approximately 10 mJ/cm² to approximately1,000 mJ/cm².

The thus obtained photoalignment film can be suitably used, for example,as the liquid crystal alignment film.

The optical film can be obtained using the liquid crystal alignment filmof the invention. The optical film is suitable for an opticalcompensation film, a phase difference plate such as a patterned phasedifference plate, or the like for realizing an improvement in contrastor extension of a viewing angle range of a liquid crystal displaydevice.

The optical film generally has the base material, the liquid crystalalignment film and an optically anisotropic layer. The opticallyanisotropic layer can be obtained by applying onto the liquid crystalalignment film formed on the base material a polymerizable liquidcrystal composition containing a polymerizable liquid crystal compound,and also various components to be added as required, and aligningmolecules of the liquid crystal compound, and then polymerizing thecompound. The optically anisotropic layer shows the optical anisotropydeveloped by alignment of the molecules of the liquid crystal compound.Therefore, the optical film can be suitably used, for example, as thepatterned phase difference plate. Such an optical film can be suitablyused for various kinds of optical devices, for example, the liquidcrystal display device.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the invention and specificexamples provided herein without departing from the spirit or scope ofthe invention. Thus, it is intended that the invention covers themodifications and variations of this invention that come within thescope of any claims and their equivalents.

The following examples are for illustrative purposes only and are notintended, nor should they be interpreted to, limit the scope of theinvention.

EXAMPLES

Hereinafter, the invention will be explained more specifically by way ofExamples, but the invention is not limited by the Examples. A structureof a compound was confirmed by a nuclear magnetic resonance spectrum.Moreover, a phase transition temperature was also measured. A unit ofthe phase transition temperature is degree Centigrade (° C.), and asymbol C stands for crystals, a symbol N stands for a nematic phase, asymbol SA stands for a smectic A phase, a symbol SB stands for a smecticB phase, and a symbol I stands for an isotropic liquid phase. In thefollowing, methods for measuring physical properties will be shown.

Preparation of Substrate with Photoalignment Film

A photoalignable polymer composition (photoaligning agent) was appliedonto a glass substrate or a TAC substrate using a spin coater or a barcoater, and then the substrate was heated at a temperature in the rangeof 60 to 130° C. for 1 to 3 minutes to remove a solvent, and thus acoating film was formed. A substrate with a photoalignment film wasprepared by irradiating a surface of the coating film with linearlypolarized ultraviolet light having a wavelength in the vicinity of 313nanometers from a direction at 90 degrees relative to an applied surfaceby means of an ultra-high-pressure mercury lamp.

Preparation of Optical Phase Difference Plate

A solution containing a polymerizable liquid crystal composition wasapplied onto a substrate with a photoalignment film, and then thesubstrate was heated at 60° C. for 1 minute, and thus a solvent wasremoved. Then, a coating film of polymerizable liquid crystals wasformed by cooling the substrate at room temperature for 1 minute. Anoptical phase difference plate was prepared by irradiating the substratewith light having an intensity of 90 mW/cm² (365 nm) using a 500 Wultra-high-pressure mercury lamp at room temperature for 30 secondsunder a nitrogen atmosphere or in atmospheric air.

Confirmation of Alignment of Liquid Crystal Molecules

A substrate with a photoalignment film, wherein polymerizable liquidcrystals were applied onto the substrate, was inserted between twopolarizing plates arranged in a crossed nicol configuration, andobserved. The substrate was rotated in a horizontal plane, and then astate of contrast and presence or absence of an alignment defect wereconfirmed.

Confirmation of Sensitivity of Photoalignment Film

Upon irradiating a substrate with a photoalignment film with linearlypolarized ultraviolet light, an optical phase difference plate wasprepared by irradiating with light having intensity in the range of 5 to100 mJ/cm² (313 nm), and then alignment of liquid crystal molecules wasconfirmed and a minimum exposure amount at which the liquid crystalmolecules align was described as alignment sensitivity.

Measurement of Weight Average Molecular Weight (Mw)

Shimadzu LC-9A Gel Permeation Chromatograph (GPC) made by ShimadzuCorporation and a column Shodex GF-7M HQ (eluent: DMF or THF, and astandard reference material: polystyrene having known molecular weight)made by Showa Denko were used.

Measurement of Film Thickness

An anisotropic polymer layer on a substrate with an anisotropic polymerwas shaved off, and a profile thereof was measured by means of a surfacetexture measuring apparatus (Alpha-Step IQ made by KLA-TencorCorporation).

Confirmation of Solubility

A photoaligning agent having a concentration of 20% by mass was dilutedwith cyclopentanone or 1-methoxy-2-propanol until a concentration of thealigning agent became 5% by mass, and solubility of a photoalignablepolymer composition was confirmed. When the solution was clouded or hada remaining solid at room temperature, the composition was evaluated tobe undissolved.

Adhesion Test

In accordance with the method as described in JIS K5400, a surface of asubstrate with optical phase difference film was cut in 100 squares in across-cut shape by using a cutter knife, a cellophane tape was onceadhered thereon, and then peeled off, and then strength of adhesion wasevaluated by expressing a ratio of the number of squares remaining onthe substrate to 100 squares as a film remaining ratio (%) (a higherremaining ratio means a higher strength of adhesion).

Preparation of Polymerizable Liquid Crystal Composition (1)

Four compounds were mixed at a ratio of compound (LC-1):compound(LC-2):compound (LC-3):compound (LC-4)=50:15:10:25 (mass ratio). Thecomposition was designated as MIX1. Based on the total mass of the MIX1,a nonionic fluorine surfactant (Futargent (registered trade name)FTX-218, made by Neos Co., Ltd.) at a mass ratio of 0.002, and apolymerization initiator Irgacure 907 (registered trade name, made byBASF Corporation) at a mass ratio of 0.06 were added thereto. A methylisobutyl ketone (MIBK) solvent was added to the composition, and thusprepared polymerizable liquid crystal composition (1) in which a ratioof the solvent was 80% by mass.

Compound (LC-1) and compound (LC-2) can be manufactured by the methoddisclosed in Makromolekulare Chemie, 190(9), 3201-3215 (1989) by Dirk J.Broer et al., or a similar method. Compound (LC-3) was manufactured inaccordance with the method described in DE 2722589 A1. Compound (LC-4)was manufactured by the method described in Makromolekulare Chemie183(10), 2311-21 (1982) by Michael Portugall et al.

Synthesis Example 1

Monomer (1-1) having a photoalignable group (as included in monomerI-1-1-a described above) was prepared as described below.

Then, 22.8 g of methoxycinnamic acid, 16.7 g of 2-hydroxybutylmethacrylate and 3.2 g of 4-dimethylaminopyridine (DMAP) were added to230 mL of dichloromethane, and the resultant mixture was stirred under anitrogen atmosphere. Thereto, a dichloromethane (60 mL) solutioncontaining 27.7 g of 1,3-dicyclohexylcarbodiimide (DCC) was addeddropwise. After dropwise addition, the resultant mixture was stirred atroom temperature for 8 hours. A precipitate formed was filtered off, andan organic layer was washed with water and dried over anhydrousmagnesium sulfate. A solvent was distilled off under reduced pressure, aresidue was purified by means of column chromatography, andrecrystallized in ethanol, and thus 30.0 g of monomer (1-1) having thephotoalignable group was obtained. Measurement results of phasetransition temperature and nuclear magnetic resonance spectrum ofmonomer (1-1) obtained were as described below.

Phase transition temperature: C 37 I.

¹H-NMR (CDCl₃; δ ppm): 7.67 (d, 1H), 7.49 (d, 2H), 6.91 (d, 2H), 6.33(d, 1H), 6.16 (s, 1H), 5.60 (s, 1H), 4.48-4.40 (m, 4H), 3.84 (s, 3H),1.96 (s, 3H).

Synthesis Example 2

Monomer (1-2) having a photoalignable group (as included in monomerI-2-1-a described above) was prepared as described below.

(First Step)

Then, 1.120 mmol of ethyl 4-hydroxycinnamate, 1.230 mmol of sodiumhydroxide and 120 mmol of sodium iodide were added to 1,000 mL ofN,N-dimethylformamide (DMF), and the resultant mixture was stirred at60° C. under a nitrogen atmosphere. Thereto, 1.230 mmol of6-chlorohexanol was added dropwise. After dropwise addition, theresultant mixture was stirred at 80° C. for 8 hours. Ethyl acetate andwater were added to a reaction mixture, and an organic layer wasextracted. The resultant organic layer was washed with water and driedover anhydrous magnesium sulfate. A solvent was distilled off underreduced pressure. The resultant residue and 1.230 mmol of sodiumhydroxide were added to a mixed solution of water (800 mL) and methanol(800 mL), and the resultant mixture was stirred for 3 hours underheating reflux. A solvent was distilled off under reduced pressure, andthe resultant residue was poured into 3 N hydrochloric acid to bereprecipitated. Crystals were filtered off and recrystallized inmethanol, and thus 840 mmol of compound (ex-1) was obtained.

(Second Step)

Then, 110 mmol of compound (ex-1), 1.100 mmol of acrylic acid and 240mmol of p-toluenesulfonic acid (p-TsOH) were added to 600 mL ofchloroform, and the resultant mixture was stirred for 8 hours whilewater was removed under heating reflux using a Dean-Stark apparatus.Water was added to a reaction mixture, and an organic layer wasextracted and dried over anhydrous magnesium sulfate. A solvent wasdistilled off under reduced pressure. The resultant residue wasrecrystallized in a mixed solvent of chloroform and methanol, and thus34 mmol of compound (ex-2) was obtained.

(Third Step)

Then, 16 mmol of compound (ex-2), 16 mmol of 4-methoxyphenol and 3 mmolof 4-dimethylaminopyridine (DMAP) were added to 50 mL ofdichloromethane, and the resultant mixture was stirred under a nitrogenatmosphere. Thereto, a dichloromethane (10 mL) solution containing 17mmol of 1,3-dicyclohexylcarbodiimide (DCC) was added dropwise. Afterdropwise addition, the resultant mixture was stirred at room temperaturefor 8 hours. A precipitate formed was filtered off, and an organic layerwas washed with water and dried over anhydrous magnesium sulfate. Asolvent was distilled off under reduced pressure, the resultant residuewas purified by means of column chromatography, and recrystallized inethanol, and thus 12 mmol of monomer (1-2) having the photoalignablegroup was obtained. Measurement results of phase transition temperatureand nuclear magnetic resonance spectrum of monomer (1-2) obtained wereas described below.

Phase transition temperature: C 64 (SB 34 SA 63) N 93 I.

¹H-NMR (CDCl₃; δ ppm): 7.81 (d, 1H), 7.52 (d, 2H), 7.07 (m, 2H), 6.92(m, 4H), 6.47 (d, 1H), 6.40 (dd, 1H), 6.12 (m, 1H), 5.82 (dd, 1H), 4.17(t, 2H), 4.00 (t, 2H), 3.81 (s, 3H), 1.79 (m, 2H), 1.70 (m, 2H),1.54-1.44 (m, 4H).

Synthesis Example 3

Monomer (1-3) having a photoalignable group (as included in monomerI-3-1-a described above) was prepared as described below.

(First Step)

Then, 50 g of 2-hydroxybutyl methacrylate and 50 mL of pyridine wereadded to 150 mL of toluene, 80 g of p-toluenesulfonic acid chloride wasadded under cooling, and the resultant mixture was stirred at roomtemperature for 16 hours under a nitrogen atmosphere. A precipitatedsalt was removed by filtration under reduced pressure. Water (100 mL)was added to a filtrate, and the resultant mixture was stirred at 40° C.for 2 hours. An organic layer was separated, and the resultant organiclayer was sequentially washed with 2 N hydrochloric acid, a saturatedaqueous solution of sodium hydrogencarbonate, and water, and dried overanhydrous magnesium sulfate. Toluene was distilled off under reducedpressure, and thus 98 g of crude colorless liquid (ex-3) was obtained.

(Final Step)

Then, 30 g of compound (ex-4) and 7.4 g of sodium hydroxide were addedto 150 mL of N,N-dimethylformamide (DMF), and the resultant mixture wasstirred at 50° C. under a nitrogen atmosphere. Thereto, 48 g of compound(ex-3) was added dropwise. After dropwise addition, the resultantmixture was stirred at 80° C. for 8 hours. After the resultant mixturewas cooled to room temperature, 200 mL of ethyl acetate and water (150mL) were added, and an organic layer was separated. A precipitate formedwas filtered off, and the resultant organic layer was washed with waterand dried over anhydrous magnesium sulfate. The resultant organic layerwas sequentially washed with 2 N hydrochloric acid, a saturated aqueoussolution of sodium hydrogencarbonate, and water, and dried overanhydrous magnesium sulfate. Ethyl acetate was distilled off underreduced pressure, the resultant residue was purified by means of columnchromatography (silica gel, eluate: toluene-ethyl acetate mixture(volume ratio: toluene/ethyl acetate=8/1)), and recrystallized inmethanol, and thus 27 g of compound (1-3) was obtained.

Measurement results of phase transition temperature and nuclear magneticresonance spectrum of compound (1-3) obtained were as described below.

Phase transition temperature: C 83 I.

¹H-NMR (CDCl₃; δ ppm): 7.65 (d, 1H), 7.48 (d, 2H), 6.92 (m, 2H), 6.32(d, 1H), 6.14 (d, 1H), 5.60 (s, 1H), 4.51 (t, 2H), 4.25 (t, 2H), 3.80(s, 3H), 1.95 (s, 3H).

Preparation Example 1 Preparation of Photoalignable Polymer (i3-1)Forming a First Component

Then, 2.10 g of monomer (1-3) having the photoalignable group obtainedin Synthesis Example 3, 0.90 g of 2-hydroxyethyl methacrylate, and 0.03g of azobisisobutyronitrile (AIBN) were added to 1-methoxy-2-propanol toprepare 15 g of solution, and the resultant mixture was stirred for 10hours under heating reflux under a nitrogen atmosphere, andpolymerization was performed. As a result, a solution of photoalignablepolymer (i3-1) was obtained. Mw of the photoalignable polymer (i3-1)obtained was 71,000.

Preparation Example 2 Preparation of Polymer (ii1-1) Having a ReactiveGroup Forming a Second Component

Then, 2.10 g of monomer (1-3) having the photoalignable group obtainedin Synthesis Example 3, 0.90 g of 3-methacryloxypropyl trimethoxysilane(Sila-Ace S710) (registered trade name, made by JNC Corporation) and0.03 g of azobisisobutyronitrile (AIBN) were added to1-methoxy-2-propanol to prepare 15 g of solution, and the resultantmixture was stirred for 10 hours under heating reflux under a nitrogenatmosphere, and polymerization was performed. As a result, a solution ofpolymer (iii-1) having a reactive group was obtained. Mw of polymer(iii-1) having the reactive group was 43,000. In addition, polymer(ii1-1) having the reactive group has a photoalignable group.

Preparation Example 3 Preparation of Polymer (ii1-2) Having a ReactiveGroup Forming a Second Component

Then, 1.50 g of monomer (1-3) having the photoalignable group obtainedin Synthesis Example 3, 0.3 g of methyl methacrylate and 1.20 g of3-methacryloxypropyl trimethoxysilane (Sila-Ace 5710) (registered tradename, made by JNC Corporation) and 0.03 g of azobisisobutyronitrile(AIBN) were added to 1-methoxy-2-propanol to prepare 15 g of solution,and the resultant mixture was stirred for 10 hours under heating refluxunder a nitrogen atmosphere, and polymerization was performed. As aresult, a solution of polymer (iii-2) having a reactive group wasobtained. Mw of polymer (ii1-2) having the reactive group was 51,000. Inaddition, polymer (ii1-2) having the reactive group has a photoalignablegroup.

Preparation Example 4 Preparation of Polymer (ii2-1) Having a ReactiveGroup Forming a Second Component

Then, 2.85 g of monomer (1-3) having the photoalignable group obtainedin Synthesis Example 3, 0.15 g of 2-methacryloiloxyethyl isocyanate(KARENZ MOIR, made by Showa Denko K. K.), and 0.03 gazobisisobutyronitrile (AIBN) were added to cyclopentanone to prepare 15g of solution, and the resultant mixture was stirred for 10 hours underheating reflux under a nitrogen atmosphere, and polymerization wasperformed. As a result, a solution of polymer (ii2-1) having a reactivegroup was obtained. Mw of polymer (ii2-1) having the reactive group was73,000. In addition, polymer (ii2-1) having the reactive group has aphotoalignable group.

Preparation Example 5 Preparation of Polymer (ii1-3) Having a ReactiveGroup Forming a Second Component

Then, 2.85 g of monomer (1-3) having the photoalignable group obtainedin Synthesis Example 3, 0.15 g of 3-methacryloxypropylmethyldimethoxysilane (KBM-502, made by Shin-Etsu Chemical Co., Ltd.) and 0.03g of azobisisobutyronitrile (AIBN) were added to cyclopentanone toprepare 15 g of solution, and the resultant mixture was stirred for 10hours under heating reflux under a nitrogen atmosphere, andpolymerization was performed. As a result, a solution of polymer (ii1-3)having a reactive group was obtained. Mw of polymer (ii1-3) having thereactive group was 96,000.

Preparation Example 6 Preparation of Photoalignable Polymer (i3-2)Forming a First Component

Then, 2.10 g of monomer (1-3) having the photoalignable group obtainedin Synthesis Example 3, 0.9 g of methyl itaconate and 0.03 g ofazobisisobutyronitrile (AIBN) were added to cyclopentanone to prepare 15g of solution, and the resultant mixture was stirred for 10 hours underheating reflux under a nitrogen atmosphere, and polymerization wasperformed. As a result, a solution of photoalignable polymer (i3-2) wasobtained. Mw of the photoalignable polymer (i3-2) obtained was 55,000.

Preparation Example 7 Preparation of Polymer (ii4-1) Having a ReactiveGroup Forming a Second Component

Then, 2.85 g of monomer (1-3) having the photoalignable group obtainedin Synthesis Example 3, 0.15 g of methyl methacrylate glycidyl ether and0.03 g of azobisisobutyronitrile (AIBN) were added to cyclopentanone toprepare 15 g of solution, and the resultant mixture was stirred for 10hours under heating reflux under a nitrogen atmosphere, andpolymerization was performed. As a result, a solution of polymer (ii4-1)having a reactive group was obtained. Mw of polymer (ii4-1) having thereactive group was 43,000. In addition, polymer (ii4-1) having thereactive group has a photoalignable group.

Example 1

Then, 0.75 g of solution of photoalignable polymer (i3-1) obtained inPreparation Example 1, 0.25 g of solution of polymer (iii-1) obtained inPreparation Example 2 and 0.005 g of p-toluenesulfonic acid hydrate weremixed to 1-methoxy-2-propanol to form a homogeneous solution, and thus4.0 g of aligning agent (H-1) containing a photoalignable polymercomposition was obtained. The photoaligning agent (H-1) was applied ontoa TAC substrate by bar coating. The substrate was heated at 60° C. for 1minute to remove a solvent, and thus a coating film was formed. Aphotoalignment film (liquid crystal alignment film) (H-2) having a filmthickness of approximately 0.2 micrometer as subjected to photoalignmenttreatment was obtained by irradiating a surface of the coating filmwith, at 10 mJ/cm², linearly polarized ultraviolet light having awavelength of approximately 313 nanometers from a direction at 90degrees relative to an applied surface by means of anultra-high-pressure mercury lamp. Onto the photoalignment film,polymerizable liquid crystal composition (1) containing polymerizableliquid crystal composition (MIX1) was applied by spin coating, then thesubstrate was heated at 60° C. for 1 minute to remove a solvent, andthus a coating film of polymerizable liquid crystals was formed. Anoptical phase difference plate (H-3) was prepared by irradiating thecoating film with light having an intensity of 90 mW/cm² (365 nm) for 30seconds. A film remaining ratio by an adhesion test on the optical phasedifference plate was 100%. Evaluation results are shown in Table 1below.

Example 2

Then, 0.90 g of solution of photoalignable polymer (i3-1) obtained inPreparation Example 1, 0.10 g of solution of polymer (ii1-2) obtained inPreparation Example 3 and 0.005 g of p-toluenesulfonic acid hydrate weremixed to 1-methoxy-2-propanol to form a homogeneous solution, and thus4.0 g of aligning agent (I-1) containing a photoalignable polymercomposition was obtained. The photoaligning agent (I-1) was applied ontoa TAC substrate by bar coating. The substrate was heated at 80° C. for 1minute to remove a solvent, and thus a coating film was formed. Aphotoalignment film (liquid crystal alignment film) (I-2) having a filmthickness of approximately 0.2 micrometer as subjected to photoalignmenttreatment was obtained by irradiating a surface of the coating filmwith, at 20 mJ/cm², linearly polarized ultraviolet light having awavelength of approximately 313 nanometers from a direction at 90degrees relative to an applied surface by means of anultra-high-pressure mercury lamp. Onto the photoalignment film,polymerizable liquid crystal composition (1) containing polymerizableliquid crystal composition (MIX1) was applied by spin coating, and thenthe substrate was heated at 60° C. for 1 minute to remove a solvent, andthus a coating film of polymerizable liquid crystals was formed. Anoptical phase difference plate (I-3) was prepared by irradiating thecoating film with light having an intensity of 90 mW/cm² (365 nm) for 30seconds. A film remaining ratio by an adhesion test on the optical phasedifference plate was 98%. Evaluation results are shown in Table 1 below.

Example 3

Then, 0.5 g of solution of photoalignable polymer (i3-1) obtained inPreparation Example 1, 0.5 g of solution of polymer (ii2-1) obtained inPreparation Example 4 and 0.002 g of p-toluenesulfonic acid hydrate weremixed to cyclopentanone to form a homogeneous solution, and thus 4.0 gof aligning agent (J-1) containing a photoalignable polymer compositionwas obtained. The photoaligning agent (J-1) was applied onto a glasssubstrate by spin coating. The substrate was heated at 100° C. for 1minute to remove a solvent, and thus a coating film was formed. Aphotoalignment film (liquid crystal alignment film) (J-2) having a filmthickness of approximately 0.2 micrometer as subjected to photoalignmenttreatment was obtained by irradiating a surface of the coating filmwith, at 5 mJ/cm², linearly polarized ultraviolet light having awavelength of approximately 313 nanometers from a direction at 90degrees relative to an applied surface by means of anultra-high-pressure mercury lamp. Onto the photoalignment film,polymerizable liquid crystal composition (1) containing polymerizableliquid crystal composition (MIX1) was applied by spin coating, and thenthe substrate was heated at 60° C. for 1 minute to remove a solvent, andthus a coating film of polymerizable liquid crystals was formed. Anoptical phase difference plate (J-3) was prepared by irradiating thecoating film with light having an intensity of 90 mW/cm² (365 nm) for 30seconds. A film remaining ratio by an adhesion test on the optical phasedifference plate was 95%. Evaluation results are shown in Table 1 below.

Example 4

Then, 0.5 g of solution of photoalignable polymer (i3-1) obtained inPreparation Example 1, 0.5 g of solution of polymer (i11-3) obtained inPreparation Example 5 and 0.002 g of p-toluenesulfonic acid hydrate weremixed to cyclopentanone to form a homogeneous solution, and thus 4.0 gof aligning agent (K-1) containing a photoalignable polymer compositionwas obtained. The photoaligning agent (K-1) was applied onto a glasssubstrate by spin coating. The substrate was heated at 100° C. for 1minute to remove a solvent, and thus a coating film was formed. Aphotoalignment film (liquid crystal alignment film) (K-2) having a filmthickness of approximately 0.2 micrometer as subjected to photoalignmenttreatment was obtained by irradiating a surface of the coating filmwith, at 5 mJ/cm², linearly polarized ultraviolet light having awavelength of approximately 313 nanometers from a direction at 90degrees relative to an applied surface by means of anultra-high-pressure mercury lamp. Onto the photoalignment film,polymerizable liquid crystal composition (1) containing polymerizableliquid crystal composition (MIX1) was applied by spin coating, and thenthe substrate was heated at 60° C. for 1 minute to remove a solvent, andthus a coating film of polymerizable liquid crystals was formed. Anoptical phase difference plate (K-3) was prepared by irradiating thecoating film with light having an intensity of 90 mW/cm² (365 nm) for 30seconds. A film remaining ratio by an adhesion test on the optical phasedifference plate was 98%. Evaluation results are shown in Table 1 below.

Example 5

Then, 0.5 g of solution of photoalignable polymer (i3-2) obtained inPreparation Example 6, and 0.5 g of solution of polymer (ii4-1) obtainedin Preparation Example 7 were mixed to cyclopentanone to form ahomogeneous solution, and thus 4.0 g of aligning agent (L-1) containinga photoalignable polymer composition was obtained. The photoaligningagent (L-1) was applied onto a glass substrate by spin coating. Thesubstrate was heated at 130° C. for 1 minute to remove a solvent, andthus a coating film was formed. A photoalignment film (liquid crystalalignment film) (L-2) having a film thickness of approximately 0.2micrometer as subjected to photoalignment treatment was obtained byirradiating a surface of the coating film with, at 5 mJ/cm², linearlypolarized ultraviolet light having a wavelength of approximately 313nanometers from a direction at 90 degrees relative to an applied surfaceby means of an ultra-high-pressure mercury lamp. Onto the photoalignmentfilm, polymerizable liquid crystal composition (1) containingpolymerizable liquid crystal composition (MIX1) was applied by spincoating, and then the substrate was heated at 60° C. for 1 minute toremove a solvent, and thus a coating film of polymerizable liquidcrystals was formed. An optical phase difference plate (L-3) wasprepared by irradiating the coating film with light having an intensityof 90 mW/cm² (365 nm) for 30 seconds. A film remaining ratio by anadhesion test on the optical phase difference plate was 100%. Evaluationresults are shown in Table 1 below.

Preparation Example 8

Then, 3.0 g of monomer (1-3) having the photoalignable group obtained inSynthesis Example 3, and 0.03 g of azobisisobutyronitrile (AIBN) wereadded to cyclopentanone to prepare 15 g of solution, the resultantmixture was stirred for 10 hours under heating reflux under a nitrogenatmosphere, and polymerization was performed. As a result, a solution ofphotoalignable polymer (M−1) was obtained. Mw of the photoalignablepolymer (M−1) obtained was 65,000. In addition, photoalignable polymer(M−1) has neither a hydroxyl group nor a carboxyl group.

Comparative Example 1

Then, 1.0 g of solution of only photoalignable polymer (i3-1) obtainedin Preparation Example 1 was mixed to 1-methoxy-2-propanol to form ahomogeneous solution, and thus 4.0 g of aligning agent (N-1) containinga photoalignable polymer was obtained. The photoaligning agent (N-1) wasapplied onto a glass substrate by spin coating. The substrate was heatedat 80° C. for 1 minute to remove a solvent, and thus a coating film wasformed. A photoalignment film (liquid crystal alignment film) (N-2)having a film thickness of approximately 0.2 micrometer as subjected tophotoalignment treatment was obtained by irradiating a surface of thecoating film with, at 20 mJ/cm², linearly polarized ultraviolet lighthaving a wavelength of approximately 313 nanometers from a direction at90 degrees relative to an applied surface by means of anultra-high-pressure mercury lamp. A film remaining ratio by an adhesiontest was 90%. A similar operation was also performed for a TACsubstrate, and a photoalignment film (liquid crystal alignment film)(N-3) having a film thickness of approximately 0.2 micrometer wasprepared by irradiating a surface of the coating film with, at 40mJ/cm², linearly polarized ultraviolet light. Onto the photoalignmentfilm, polymerizable liquid crystal composition (1) containingpolymerizable liquid crystal composition (MIX1) was applied by spincoating, then the substrate was heated at 60° C. for 1 minute to removea solvent, and thus a coating film of polymerizable liquid crystals wasformed. An optical phase difference plate (N-4) was prepared byirradiating the coating film with light having an intensity of 90 mW/cm²(365 nm) for 30 seconds. A film remaining ratio by an adhesion test onthe optical phase difference plate was 70%. Evaluation results are shownin Table 1 below.

Comparative Example 2

Then, 1.0 g of solution of only photoalignable polymer (M−1) obtained inPreparation Example 8 was mixed to cyclopentanone to form a homogeneoussolution, and thus 4.0 g of aligning agent (O-1) containing aphotoalignable polymer was obtained. The photoaligning agent (O-1) wasapplied onto a glass substrate by spin coating. The substrate was heatedat 80° C. for 1 minute to remove a solvent, and thus a coating film wasformed. A photoalignment film (liquid crystal alignment film) (O-2)having a film thickness of approximately 0.2 micrometer as subjected tophotoalignment treatment was obtained by irradiating a surface of thecoating film with, at 10 mJ/cm², linearly polarized ultraviolet lighthaving a wavelength of approximately 313 nanometers from a direction at90 degrees relative to an applied surface by means of anultra-high-pressure mercury lamp. Onto the photoalignment film,polymerizable liquid crystal composition (1) containing polymerizableliquid crystal composition (MIX1) was applied by spin coating, then thesubstrate was heated at 60° C. for 1 minute to remove a solvent, andthus a coating film of polymerizable liquid crystals was formed. Anoptical phase difference plate (O-3) was prepared by irradiating thecoating film with light having an intensity of 90 mW/cm² (365 nm) for 30seconds. A film remaining ratio by an adhesion test on the optical phasedifference plate was 5%. A similar operation was also performed for aTAC substrate, and a photoalignment film (O-4) was prepared byirradiating the coating film with, at 50 mJ/cm², linearly polarizedultraviolet light. Onto the photoalignment film, polymerizable liquidcrystal composition (1) containing polymerizable liquid crystalcomposition (MIX1) was applied by spin coating, then the substrate washeated at 60° C. for 1 minute to remove a solvent, and thus a coatingfilm of polymerizable liquid crystals was formed. Light having anintensity of 90 mW/cm² (365 nm) was irradiated to the coating film for30 seconds, but the substrate (0-5) showed no liquid crystal alignmentproperties. Evaluation results are shown in Table 1 below.

Comparative Example 3

Then, 1.0 g of solution of photoalignable polymer (i3-2) obtained inPreparation Example 6 was mixed to cyclopentanone to form a homogeneoussolution, and thus 4 g of aligning agent (P-1) containing aphotoalignable polymer was obtained. The photoaligning agent (P-1) wasapplied onto a glass substrate by spin coating. The substrate was heatedat 80° C. for 1 minute to remove a solvent, and thus a coating film wasformed. A photoalignment film (liquid crystal alignment film) (P-2)having a film thickness of approximately 0.2 micrometer as subjected tophotoalignment treatment was obtained by irradiating a surface of thecoating film with, at 20 mJ/cm², linearly polarized ultraviolet lighthaving a wavelength of approximately 313 nanometers from a direction at90 degrees relative to an applied surface by means of anultra-high-pressure mercury lamp. Onto the photoalignment film,polymerizable liquid crystal composition (1) containing polymerizableliquid crystal composition (MIX1) was applied by spin coating, then thesubstrate was heated at 60° C. for 1 minute to remove a solvent, andthus a coating film of polymerizable liquid crystals was formed. Anoptical phase difference plate (P-3) was prepared by irradiating thecoating film with light having an intensity of 90 mW/cm² (365 nm) for 30seconds. A film remaining ratio by an adhesion test on the optical phasedifference plate was 90%. A similar operation was also performed for aTAC substrate, and a photoalignment film (P-4) was prepared byirradiating the coating film with, at 50 mJ/cm², linearly polarizedultraviolet light. Onto the photoalignment film, polymerizable liquidcrystal composition (1) containing polymerizable liquid crystalcomposition (MIX1) was applied by spin coating, then the substrate washeated at 60° C. for 1 minute to remove a solvent, and thus a coatingfilm of polymerizable liquid crystals was formed. Light having anintensity of 90 mW/cm² (365 nm) was irradiated to the coating film for30 seconds, but the substrate (P-5) showed no liquid crystal alignmentproperties. Evaluation results are shown in Table 1 below.

TABLE 1 Polymer Polymer Baking Sensitivity Adhesion test (1) (2)Substrate temperature mJ/cm² (glass substrate) Example 1 i3-1 ii1-1 TAC 60° C. 10 100%  Example 2 i3-1 ii1-2 TAC  80° C. 20 98% Example 3 i3-1li2-1 Glass 100° C.  5 95% Example 4 i3-1 ii1-3 Glass 100° C.  5 98%Example 5 i3-2 ii4-1 Glass 130° C. 10 100%  Comparative i3-1 Glass  80°C. 20 90% Example 1 TAC 100° C. 40 70% Comparative M-1 Glass  80° C. 10 5% Example 2 TAC 100° C. No alignment — Comparative i3-2 Glass 130° C.30 90% Example 3 TAC 100° C. No alignment —

Although the invention has been described and illustrated with a certaindegree of particularity, it is understood that the disclosure has beenmade only by way of example, and that numerous changes in the conditionsand order of steps can be resorted to by those skilled in the artwithout departing from the spirit and scope of the invention.

INDUSTRIAL APPLICABILITY

A photoalignable polymer composition of the invention contains the firstcomponent being a photoalignable polymer and the second component beinga polymer that is reactive with the first component. Therefore, aphotoalignable film obtained by applying a photoaligning agentcontaining the composition to a base material or the like and drying theapplied composition thereon is excellent in sensitivity to allowphotoalignment even with exposure in a short period of time. Thus, thecomposition is suitable for a photoalignment method. Moreover, a liquidcrystal alignment film obtained using the photoalignable polymercomposition of the invention requires no rubbing treatment, andtherefore has no alignment defect and allows a uniform alignment ofliquid crystal molecules. Therefore, the liquid crystal alignment filmis suitable for use in the form of an optical film or an optical devicesuch as a liquid crystal display device.

What is claimed is:
 1. A photoalignable polymer composition, containingas a first component a photoalignable polymer having at least onephotoalignable group and at least one polar group selected from ahydroxyl group and a carboxyl group and having none of a group which isreactive with the polar group, and as a second component a polymerhaving a group that is reactive with the polar group.
 2. Thephotoalignable polymer composition according to claim 1, wherein thepolymer of the second component further has a photoalignable group. 3.The photoalignable polymer composition according to claim 1, wherein thephotoalignable group included in the photoalignable polymer of the firstcomponent has at least one kind of structures represented by formulas(I-1) to (I-3) below:

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 5 carbons in which arbitrary hydrogen may be replaced byfluorine, m represents 2, 4 or 6, and arbitrary hydrogen of a phenylenegroup may be replaced by fluorine, a methyl group or a methoxy group. 4.The photoalignable polymer composition according to claim 1, wherein thegroup that is included in the polymer of the second component and reactswith at least one polar group selected from the hydroxyl group and thecarboxyl group is at least one group selected from an alkoxysilanegroup, an isocyanate group, a [1′-methylpropylideneamino]carboxyaminogroup, a (3,5-dimethylpyrazolyl)carbonylamino group and an epoxy group.5. The photoalignable polymer composition according to claim 4, whereinthe group that is included in the polymer of the second component andreacts with at least one polar group selected from the hydroxyl groupand the carboxyl group is an alkoxysilane group.
 6. The photoalignablepolymer composition according to claim 5, wherein the polymer of thesecond component includes at least one kind of constitutional unitrepresented by formula (II-1-1) below:

wherein, in the formulas, R³ represents hydrogen, an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine,or an alkoxy group having 1 to 20 carbons in which arbitrary hydrogenmay be replaced by fluorine, R² each independently represents hydrogen,an alkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction. 7.The photoalignable polymer composition according to claim 1, wherein thephotoalignable polymer of the first component includes a constitutionalunit derived from a monomer having a photoalignable group, and aconstitutional unit derived from at least one kind of monomer selectedfrom the group of acrylic acid, methacrylic acid,hydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 tocarbons, carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and a phenolic hydroxyl group-containing(meth)acrylate.
 8. The photoalignable polymer composition according toclaim 7, wherein the photoalignable polymer of the first componentincludes at least one kind of constitutional unit represented byformulas (I-1-1) to (I-3-1) below, and at least one kind ofconstitutional unit derived from hydroxyalkyl(meth)acrylate having ahydroxyalkyl group having 2 to 6 carbons:

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —OCO—, o represents an integer from 2 to 10, p represents an integerfrom 0 to 2, r represents 0 or 1, y¹, y² and y³ are a mole fraction andsatisfy a relationship (0<y¹+y²+y³<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or
 1. 9. The photoalignable polymer composition accordingto claim 7, wherein the photoalignable polymer of the first componentincludes at least one kind of constitutional unit represented byformulas (I-1-1) to (I-3-1) below, and a constitutional unit derivedfrom at least one kind of monomer selected from carboxylgroup-containing (meth)acrylate, carboxyl group-containing itaconate andphenolic hydroxyl group-containing (meth)acrylate:

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —OCO—, o is an integer from 2 to 10, p is an integer from 0 to 2, rrepresents 0 or 1, y¹, y² and y³ are a mole fraction and satisfy arelationship (0<y¹+y²+y³<1), and arbitrary hydrogen of a phenylene groupmay be replaced by fluorine, a methyl group or a methoxy group:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or
 1. 10. The photoalignable polymer composition accordingto claim 8, wherein the photoalignable polymer of the first componentincludes at least one kind of constitutional unit represented by formula(I-2-1) below, and a constitutional unit derived fromhydroxyalkyl(meth)acrylate having a hydroxyalkyl group having 2 to 6carbons, and the polymer of the second component includes aconstitutional unit represented by formula (II-1-1) below:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, ora group represented by formula (I-4) below, R⁷ represents hydrogen, analkyl group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine or an alkoxy group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine, Z¹ represents a singlebond, —COO— or —OCO—, o represents an integer from 2 to 10, p representsan integer from 0 to 2, r represents 0 or 1, y is a mole fraction(satisfying a relationship: 0<y<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.11. The photoalignable polymer composition according to claim 8, whereinthe photoalignable polymer of the first component includes at least onekind of constitutional unit represented by formula (I-3-1) below, and aconstitutional unit derived from hydroxyalkyl(meth)acrylate having ahydroxyalkyl group having 2 to 6 carbons, and the polymer of the secondcomponent includes a constitutional unit represented by formula (II-1-1)below:

wherein, in the formula, R¹ represents hydrogen or an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine,R³ represents hydrogen, an alkyl group having 1 to 5 carbons in whicharbitrary hydrogen may be replaced by fluorine, or a group representedby formula (I-4) below, Z¹ represents a single bond, —COO— or —OCO—, orepresents an integer from 2 to 10, p represents an integer from 0 to 2,r represents 0 or 1, y is a mole fraction (satisfying a relationship:0<y<1), and arbitrary hydrogen of a phenylene group may be replaced byfluorine, a methyl group or a methoxy group:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.12. The photoalignable polymer composition according to claim 9, whereinthe photoalignable polymer of the first component includes at least onekind of constitutional unit represented by formula (I-1-1) below, and aconstitutional unit derived from at least one kind of monomer selectedfrom carboxyl group-containing (meth)acrylate, carboxyl group-containingitaconate and phenolic hydroxyl group-containing (meth)acrylate, and thepolymer of the second component includes a constitutional unitrepresented by formula (II-1-1) below:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, ora group represented by formula (I-4) below, R⁷ represents hydrogen, analkyl group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine or an alkoxy group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine, Z¹ represents a singlebond, —COO— or —OCO—, o represents an integer from 2 to 10, p representsan integer from 0 to 2, r represents 0 or 1, y is a mole fraction(satisfying a relationship: 0<y<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.13. The photoalignable polymer composition according to claim 9, whereinthe photoalignable polymer of the first component includes at least onekind of constitutional unit represented by formula (I-2-1) below, and aconstitutional unit derived from at least one kind of monomer selectedfrom carboxyl group-containing (meth)acrylate, carboxyl group-containingitaconate and phenolic hydroxyl group-containing (meth)acrylate, and thepolymer of the second component includes a constitutional unitrepresented by formula (II-1-1) below:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 5 carbons in which arbitrary hydrogen may be replaced by fluorine, ora group represented by formula (I-4) below, R⁷ represents hydrogen, analkyl group having 1 to 20 carbons in which arbitrary hydrogen may bereplaced by fluorine or an alkoxy group having 1 to 20 carbons in whicharbitrary hydrogen may be replaced by fluorine, Z′ represents a singlebond, —COO— or —OCO—, o represents an integer from 2 to 10, p representsan integer from 0 to 2, r represents 0 or 1, y is a mole fraction(satisfying a relationship: 0<y<1), and arbitrary hydrogen of aphenylene group may be replaced by fluorine, a methyl group or a methoxygroup:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.14. The photoalignable polymer composition according to claim 9, whereinthe photoalignable polymer of the first component includes at least onekind of constitutional unit represented by formula (I-3-1) below, and aconstitutional unit derived from at least one kind of monomer selectedfrom carboxyl group-containing (meth)acrylate, carboxyl group-containingitaconate and phenolic hydroxyl group-containing (meth)acrylate, and thepolymer of the second component includes a constitutional unitrepresented by formula (II-1-1) below:

wherein, in the formula, R¹ represents hydrogen or an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorine,R³ represents hydrogen, an alkyl group having 1 to 5 carbons in whicharbitrary hydrogen may be replaced by fluorine, or a group representedby formula (I-4) below, Z¹ represents a single bond, —COO— or —OCO—, orepresents an integer from 2 to 10, p represents an integer from 0 to 2,r represents 0 or 1, y is a mole fraction (satisfying a relationship:0<y<1), and arbitrary hydrogen of a phenylene group may be replaced byfluorine, a methyl group or a methoxy group:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, R² each independently represents hydrogen, analkyl group having 1 to 4 carbons or an alkoxy group having 1 to 4carbons, at least one of R² is an alkoxy group having 1 to 4 carbons, qrepresents an integer from 0 to 10, and x represents a mole fraction.15. The photoalignable polymer composition according to claim 8, whereinthe photoalignable polymer of the first component includes at least onekind of constitutional unit represented by formulas (I-1-1) to (I-3-1)below, and a constitutional unit derived from hydroxyalkyl(meth)acrylatehaving a hydroxyalkyl group having 2 to 6 carbons, and the polymer ofthe second component includes a constitutional unit represented byformula (II-2-1) or (II-3-1):

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —OCO—, o is an integer from 2 to 10, p is an integer from 0 to 2, rrepresents 0 or 1, y¹, y² and y³ are a mole fraction and satisfy arelationship (0<y¹+y²+y³<1), and arbitrary hydrogen of a phenylene groupmay be replaced by fluorine, a methyl group or a methoxy group:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formula, R³ represents hydrogen, an alkyl group having 1to 20 carbons in which arbitrary hydrogen may be replaced by fluorine oran alkoxy group having 1 to 20 carbons in which arbitrary hydrogen maybe replaced by fluorine, L represents —CH₂CH₂— or —CH₂CH₂OCH₂CH₂—, R⁴represents a group represented by formula (II-3-1-1) or (II-3-1-2)below, and z represents a mole fraction:


16. The photoalignable polymer composition according to claim 9, whereinthe photoalignable polymer of the first component includes at least onekind of constitutional unit represented by formulas (I-1-1) to (I-3-1)below, and a constitutional unit derived from at least one kind ofmonomer selected from carboxyl group-containing (meth)acrylate, carboxylgroup-containing itaconate and phenolic hydroxyl group-containing(meth)acrylate, and the polymer of the second component includes aconstitutional unit represented by formula (II-4-1) below:

wherein, in the formulas, R¹ represents hydrogen or an alkyl grouphaving 1 to 20 carbons in which arbitrary hydrogen may be replaced byfluorine, R³ represents hydrogen, an alkyl group having 1 to 5 carbonsin which arbitrary hydrogen may be replaced by fluorine, or a grouprepresented by formula (I-4) below, R⁷ represents hydrogen, an alkylgroup having 1 to 20 carbons in which arbitrary hydrogen may be replacedby fluorine or an alkoxy group having 1 to 20 carbons in which arbitraryhydrogen may be replaced by fluorine, Z¹ represents a single bond, —COO—or —OCO—, o is an integer from 2 to 10, p is an integer from 0 to 2, rrepresents 0 or 1, y¹, y² and y³ are a mole fraction and satisfy arelationship (0<y¹+y²+y³<1), and arbitrary hydrogen of a phenylene groupmay be replaced by fluorine, a methyl group or a methoxy group:

wherein, in the formula, R⁸ represents hydrogen or a methyl group, and grepresents 0 or 1:

wherein, in the formulas, R³ represents hydrogen, an alkyl group having1 to 20 carbons in which arbitrary hydrogen may be replaced by fluorineor an alkoxy group having 1 to 20 carbons in which arbitrary hydrogenmay be replaced by fluorine, T represents a methylene group having 1 to20 carbons in which oxygen may be substituted for arbitrary carbon(however, oxygen is not substituted for adjacent carbonssimultaneously), S represents a group represented by formula (II-4-1-1),(II-4-1-2) or (II-4-1-3), R⁸ represents a methyl group or an ethylgroup, and w represents a mole fraction.
 17. The photoalignable polymercomposition according to claim 1, wherein a ratio of the first componentis in the range of 50.00 to 99.99% by mass and a ratio of the secondcomponent is in the range of 0.01 to 50.00% by mass, based on the totalmass of the first component and the second component.
 18. Thephotoalignable polymer composition according to claim 1, wherein a ratioof the first component is in the range of 70.00 to 99.50% by mass and aratio of the second component is in the range of 0.50 to 30.00% by mass,based on the total mass of the first component and the second component.19. The photoalignable polymer composition according to any one of claim1, containing at least one kind of material selected from a sensitizerand a crosslinking agent in the range of 0.01 to 50% by mass based onthe total mass of the first component and the second component.
 20. Thephotoalignable polymer composition according to claim 1, containing atleast one kind of material selected from an acid compound, a thermalacid generator and a photoacid generator in the range of 0.01 to 50% bymass based on the total mass of the first component and the secondcomponent.
 21. The photoalignable polymer composition according to claim1, further containing a glycol solvent or a glycol ether solvent thatcan dissolve the first component and the second component.
 22. A liquidcrystal alignment film formed of the photoalignable polymer compositionaccording to claim
 1. 23. An optical device, comprising a phasedifference plate prepared using the photoalignable polymer compositionaccording to claim
 1. 24. A patterned phase difference plate preparedfrom the photoalignable polymer composition according to claim 1.